Amide compound and its production and use

ABSTRACT

The present invention relates to certain novel amide compound represented by the formula of ##STR1## wherein A, X, Y, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7  and l are the same as defined in the present specification, an insecticidal and/or acaricidal composition containing it as an active ingredient, and a method for exterminating insects and/or acarids which comprises applying it as an active ingredient.

This application is a continuation-in-part of U.S. patent applicationSer. No. 07/506336 filed on Apr. 9, 1990 now abandoned.

The present invention relates to a novel amide compound, its production,and insecticidal and acaricidal composition containing it as an activeingredient.

It has been disclosed in the specifications of EP-289879-A andEP-307801-A that certain kinds of amide compounds have an insecticidal,acaricidal activities.

These compounds are, however, not necessarily sufficient in view oftheir activities, spectra and others.

Under such circumstances, the present inventors have made extensiveresearch to develop compounds having an excellent insecticidal,acaricidal activities, and resultantly have found that amide compoundsrepresented by the later-mentioned formula [I] have excellentinsecticidal, acaricidal activities, and have accomplished the presentinvention.

The present invention provides an amide compound represented by theformula [I] [hereinafter referred to as the compound of the presentinvention], its production, and insecticidal and acaricidal compositioncontaining it as an active ingredient:

An amide compound represented by the formula [I] of ##STR2## wherein R¹is a hydrogen atom, an alkyl group of 1-4 carbons or a haloalkyl groupof 1-4 carbons; R² and R³ independently are a hydrogen atom, a halogenatom, an alkyl group of 1-6 carbons, a cycloalkyl group of 3-6 carbons,a haloalkyl group of 1-6 carbons, a phenyl group or an alkoxy group of1-6 carbons, R⁴ is a hydrogen atom, an alkyl group of 1-4 carbons or agroup represented by the formula of

    --S(O).sub.m R.sup.11 ;

R⁵ is a hydrogen atom, an alkyl group of 1-4 carbons or a cyano group;

R⁶ is a hydrogen atom or an alkyl group of 1-4 carbons;

R⁷ is a hydrogen atom, a halogen atom or an alkyl group of 1-4 carbons,provided that when l is an integer of 2, each of R⁷ s may be the same ordifferent from each other;

A is the group represented by the formula of ##STR3##

R⁸ is a halogen atom, an alkyl group of 1-8 carbons, a haloalkyl groupof 1-8 carbons, a haloalkoxy group of 1-8 carbons, an alkylthio group of1-8 carbons, a haloalkylthio group of 1-8 carbons, an alkenylthio groupof 2-8 carbons, a haloalkenylthio group of 2-8 carbons, an alkynylthiogroup of 2-8 carbons, an alkylsulfinyl group of 1-8 carbons, analkylsulfonyl group of 1-8 carbons;

R⁹ is a haloalkoxy group of 1-8 carbons, an alkylthio group of 1-8carbons, a haloalkylthio group of 1-8 carbons, an alkenylthio group of2-8 carbons, a haloalkenylthio group of 2-8 carbons, an alkynylthiogroup of 2-8 carbons, an alkylsulfinyl group of 1-8 carbons, analkylsulfonyl group of 1-8 carbons;

R¹⁰ is a halogen atom, an alkyl group of 1-8 carbons, a haloalkyl groupof 1-8 carbons, provided that two of R¹⁰ may be the same or differentfrom each other; provided that R⁸ and R¹⁰ may be linked at their ends,when they are adjacent each other, to form a saturated five-memberedring which contains 0-2 oxygen atoms therein; R¹¹ is an alkyl group of1-18 carbons, a haloalkyl group of 1-18 carbons, or a group representedby the formula of ##STR4## or the formula of ##STR5##

R¹² is a hydrogen atom, an alkyl group of 1-4 carbons or a haloalkylgroup of 1-4 carbons;

R¹³ is a hydrogen atom, a halogen atom, an alkyl group of 1-4 carbons, ahaloalkyl group of 1-4 carbons, an alkoxy group of 1-4 carbons, ahaloalkoxy group of 1-4 carbons, an alkylthio group of 1-4 carbons, ahaloalkylthio group of 1-4 carbons, an alkylsulfinyl group of 1-4carbons, a haloalkylsulfinyl group of 1-4 carbons, an alkylsulfonylgroup of 1-4 carbons, a haloalkylsulfonyl group of 1-4 carbons, analkylsulfonyloxy group of 1-4 carbons, a haloalkylsulfonyloxy group of1-4 carbons, nitro or cyano group, provided that when p is an integer of2 to 5, each of R¹³ s may be the same or different from each other;

R¹⁴ is an alkyl group of 1-8 carbons, a haloalkyl group of 1-8 carbons,an alkoxyalkyl group of 3-8 total carbons or a (haloalkoxy)alkyl groupof 3-8 total carbons;

R¹⁵ is an alkyl group of 1-8 carbons, a haloalkyl group of 1-8 carbons,an alkoxyalkyl group of 3-8 total carbons, a (haloalkoxy)alkyl group of3-8 total carbons or a group represented by the formula of ##STR6##provided that R¹⁴ and R¹⁵ may be linked at their ends to form asaturated or unsaturated five- or six-membered ring which contains 0-2oxygen or sulfur atoms therein and may be substituted with a halogenatom, an alkyl group of 1-4 carbons, an alkoxy group of 1-4 carbons oran alkylthio group of 1-4 carbons;

R¹⁶ is a hydrogen atom, an alkyl group of 1-8 carbons, a haloalkyl groupof 1-8 carbons, an alkoxyalkyl group of 2-8 total carbons or a(haloalkoxy)alkyl group of 2-8 total carbons; R¹⁷ is an alkyl group of1-18 carbons, a haloalkyl group of 1-18 carbons, an alkoxyalkyl group of3-18 total carbons, a (haloalkoxy)-alkyl group of 3-18 total carbons, analkoxyhaloalkyl group of 3-18 total carbons, an alkylthioalkyl group of3-18 total carbons, a (haloalkylthio)alkyl group of 3-18 total carbons,a cycloalkyl group of 3-8 carbons which may be substituted with an alkylgroup of 1-10 carbons, a cycloalkyl group of 3-8 carbons substitutedwith a haloalkyl group of 1-10 carbons, a halocycloalkyl group of 3-8carbons which may be substituted with an alkyl group of 1-10 carbons, acycloalkyl group of 3-8 carbons substituted with an alkoxy group of 1-10carbons, or a cycloalkyl group of 3-8 carbons substituted with ahaloalkoxy group of 1-10 carbons;

W is an oxygen atom, a sulfur atom, a sulfinyl group or single bond;

l is an integer of 1 or 2;

m is an integer of 0-2;

n is an integer of 1-4;

p is an integer of 1-5;

q is an integer of 0-10;

X is an oxygen atom or a sulfur atom; Y is an oxygen atom, a sulfuratom, a sulfinyl, sulfonyl or methylene group.

In the compounds of the present invention represented by the formula(I), the alkyl group of 1-4 carbons denoted by R¹ includes, for example,methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and the like; andthe haloalkyl group of 1-8 carbons includes, for example,trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 1-fluoroethyl,1,2-difluoroethyl, 3-fluoropropyl, 1-fluoropropyl, 2-fluoropropyl,4-fluorobutyl, 2-chloroethyl, 3-chloropropyl, 4-chlorobutyl,3-bromopropyl and the like.

The halogen atom denoted by R² or R³ includes, for example, fluorineatom, chlorine atom, bromine atom and the like; the alkyl group of 1-6carbons includes, for example, methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, neopentyl and thelike; cycloalkyl group of 3-6 carbons includes, for example,cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyland the like; and the haloalkyl group of 1-6 carbons includes, forexample, fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl,2,2,2-trifluoroethyl, 1,2,2,2-tetrafluoroethyl,1,1,2,2-tetrafluoroethyl, 2,2,3,3-tetrafluoropropyl,2,2,3,3,3-pentafluoropropyl and the like.

The alkoxyl group of 1-6 carbons includes, for example, methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, n-amyloxy,neopentyloxy, n-hexyloxy and the like; and the haloalkoxyl group of 1-6carbons includes, for example, difluoromethoxy, 2-fluoroethoxy,2,2,2-trifuoroethoxy and the like; and the cycloalkoxy group of 3-6carbons includes, for example, cyclopropyloxy, 1-methylcyclopropyloxy,cyclobutyloxy, cyclopentyloxy, cyclohexyloxy and the like.

The alkyl group of 1-4 carbons denoted by R⁴ includes, for example,methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and thelike. The alkyl group of 1-4 carbons denoted by R⁵ or R⁶ includes, forexample, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,isobutyl and the like. The halogen atom denoted by R⁷ includes, forexample, a fluorine atom, chlorine atom, bromine atom and the like; andthe alkyl group of 1-4 carbons includes, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and the like. Thehalogen atom denoted by R⁸ includes, for example, fluorine atom,chlorine atom, bromine atom and the like; the alkyl group of 1-8 carbonsincludes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, isobutyl, tert-butyl, n-amyl, neopentyl, n-hexyl, n-heptyl,n-octyl and the like; the haloalkyl group of 1-8 carbons includes, forexample, difluoromethyl, trifluoromethyl, 2-fluoroethyl,2,2,2-trifluoroethyl, 1-fluoroethyl, 1,2-difluoroethyl, 3-fluoropropyl,1-fluoropropyl, 2-fluoropropyl, 4-fluorobutyl, 5-fluoroamyl,6-fluorohexyl, 7-fluoroheptyl, 8-fluorooctyl, 2-chloroethyl,3-chloropropyl, 4-chlorobutyl, 3-bromopropyl and the like; thehaloalkoxyl group of 1-8 carbons includes, for example, difluoromethoxy,trifluoromethoxy, 2-fluoroethoxy, 2,2,2-trifluoroethoxy,1,1,2,2-tetrafluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy,2,2-dichloro-1,1-difluoroethoxy, 2,2,3,3,3-pentafluoropropyloxy,1,1,1,3,3,3-hexafluoro-2-propyloxy, 1,1,2,3,3,3-hexafluoropropyloxy,3,3,4,4,4-pentafluoro-2-butyloxy, 3-fluoropropyloxy, 4 -fluorobutyloxy,5-fluoroamyloxy, 6-fluorohexyloxy, 7-fluoroheptyloxy, 8-fluorooctyloxy,2-chloroethoxy, 3-chloropropoxy, 4-chlorobutyloxy, 3-bromopropoxy andthe like; the alkylthio group of 1-8 carbons includes, for example,methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio,isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio,isopentylthio, secpentylthio, 2-ethylpropylthio, n-hexylthio,n-heptylthio, n-octylthio and the like: the haloalkylthio group of 1-8carbons includes, for example, fluoromethylthio, difluoromethylthio,trifluoromethylthio, 2-fluoroethylthio, 2,2,2-trifluoroethylthio,1,1,2,2-tetrafluoroethylthio, 2-chloro-1,1,2-trifluoroethylthio,2,2-dichloro-1,1-difluoroethylthio, 2,2,3,3,3-pentafluoropropylthio,1,1,1,3,3,3-hexafluoro-2-propylthio, 1,1,2,3,3,3-hexafluoropropylthio,3,3,4,4,4-pentafluoro-2-butylthio, 3-fluoropropylthio,4-fluorobutylthio, 5-fluoroamylthio, 6-fluorohexylthio,7-fluoroheptylthio, 8-fluorooctylthio, 2-chloroethylthio,3-chloropropylthio, 4-chlorobutylthio, 3-bromopropylthio and the like;the alkenylthio group of 2-8 carbons includes, for example, vinylthio,allylthio, 1-propenylthio, 2-butenylthio, 2-methyl-2-propenylthio,2-pentenylthio, 3-methyl-2-butenylthio, 2-hexenylthio, 2-heptenylthio,2-octenylthio and the like; the alkynylthio group of 2-8 carbonsincludes, for example, ethynylthio, propargylthio,1-methylpropargylthio, 1-propynylthio, 2-butynylthio,4,4-dimethyl-2-pentynylthio, 2-pentynylthio, 2-hexynylthio,2-heptynylthio, 2-octynylthio and the like; the haloalkenylthio9 groupof 2-8 carbons includes, for example, 1,2-dichlorovinylthio,2,3-dichloroallylthio, 2-iodo-1-fluorovinylthio,2-chloro-1-fluorovinylthio, 2,2-dichloro-1-fluorovinylthio,2,2-dichloro-vinylthio and the like; the alkylsulfinyl group of 1-8carbons includes, for example, methylsulfinyl, ethylsulfinyl,n-propylsulfinyl, 2-propylsulfinyl, n-butylsulfinyl, 2-butylsulfinyl,2-methylpropylsulfinyl, 1,1-dimethylethylsulfinyl, n-pentylsulfinyl,2-pentylsulfinyl, 3-methylbutylsulfinyl, 2-ethylpropylsulfinyl,n-hexylsulfinyl, n-heptylsulfinyl, n-octylsulfinyl and the like; thealkylsulfonyl group of 1-8 carbons includes, for example,methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 2-propylsulfonyl,n-butylsulfonyl, 2-butylsulfonyl, 2-methylpropylsulfonyl,1,1-dimethylethylsulfonyl, n-pentylsulfonyl, 2-pentylsulfonyl,3-methylbutylsulfonyl, 2-ethylpropylsulfonyl, n-hexylsulfonyl,n-heptylsulfonyl, n-octylsulfonyl and the like; The haloalkoxy group of1-8 carbons denoted by R⁹ includes, for example, difluoromethoxy,trifluoromethoxy, 2-fluoroethoxy, 2,2,2-trifluoroethoxy,1,1,2,2-tetrafluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy,2,2-dichloro-1,1-difluoroethoxy, 2,2,3,3,3-pentafluoropropyloxy,1,1,1,3,3,3-hexafluoro-2-propyloxy, 1,1,2,3,3,3-hexafluoropropyloxy,3,3,4,4,4-pentafluoro-2-butyloxy, 3-fluoropropyloxy, 4-fluorobutyloxy,5-fluoroamyloxy, 6-fluorohexyloxy, 7-fluoroheptyloxy, 8-fluorooctyloxy,2-chloroethoxy, 3-chloropropoxy, 4-chlorobutyloxy, 3-bromopropoxy andthe like; the alkylthio group of 1-8 carbons includes, for example,methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio,isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio,isopentylthio, sec-pentylthio, 2-ethylpropylthio, n-hexylthio,n-heptylthio, n-octylthio and the like; the haloalkylthio group of 1-8carbons includes, for example, fluoromethylthio, difluoromethylthio,trifluoromethylthio, 2-fluoroethylthio, 2,2,2-trifluoroethylthio,1,1,2,2-tetrafluoroethylthio, 2-chloro-1,1,2-trifluoroethylthio,2,2-dichloro-1,1-difluoroethylthio, 2,2,3,3,3-pentafluoropropylthio,1,1,1,3,3,3-hexafluoro-2-propylthio, 1,1,2,3,3,3-hexafluoropropylthio,3,3,4,4,4-pentafluoro-2-butylthio, 3-fluoropropylthio,4-fluorobutylthio, 5-fluoroamylthio, 6-fluorohexylthio,7-fluoroheptylthio, 8-fluorooctylthio, 2-chloroethylthio,3-chloropropylthio, 4-chlorobutylthio, 3-bromopropylthio and the like;the alkenylthio group of 2-8 carbons includes, for example, vinylthio,allylthio, 1-propenylthio, 2-butenylthio, 2-methyl-2-propenylthio,2-pentenylthio, 3-methyl-2-butenylthio, 2-hexenylthio, 2-heptenylthio,2-octenylthio and the like: the alkynylthio group of 2-8 carbonsincludes, for example, ethynylthio, propargylthio,1-methylpropargylthio, 1-propynylthio, 2-butynylthio,4,4-dimethyl-2-pentynylthio, 2-pentynylthio, 2-hexynylthio,2-heptynylthio, 2-octynylthio and the like; the haloalkenylthio group of2-8 carbons includes, for example, 1,2-dichlorovinylthio,2,3-dichloroallylthio, 2-iodo-1-fluorovinylthio,2-chloro-1-fluorovinylthio, 2,2-dichloro-1-fluorovinylthio,2,2-dichloro-vinylthio and the like; the alkylsulfinyl group of 1-8carbons includes, for example, methylsulfinyl, ethylsulfinyl,n-propylsulfinyl, 2-propylsulfinyl, n-butylsulfinyl, 2-butylsulfinyl,2-methylpropylsulfinyl, 1,1-dimethylethylsulfinyl, n-pentylsulfinyl,2-pentylsulfinyl, 3-methylbutylsulfinyl, 2-ethylpropylsulfinyl,n-hexylsulfinyl, n-heptylsulfinyl, n-octylsulfinyl and the like; thealkylsulfonyl group of 1-8 carbons includes, for example,methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 2-propylsulfonyl,n-butylsulfonyl, 2-butylsulfonyl, 2-methylpropylsulfonyl,1,1-dimethylethylsulfonyl, n-pentylsulfonyl, 2-pentylsulfonyl,3-methylbutylsulfonyl, 2-ethylpropylsulfonyl, n-hexylsulfonyl,n-heptylsulfonyl, n-octylsulfonyl and the like; the alkyl group of 1-18carbons denoted by R⁷ includes, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, neo-pentyl,tert-pentyl, 1-methylbutyl, n-hexyl, n-heptyl, n-octyl, 1-methylheptyl,n-dodecyl, n-hexadecyl, n-octadecyl and the like; and the haloalkylgroup of 1-18 carbons includes, for example, trifluoromethyl,2-fluoroethyl, 2,2,2-trifluoroethyl, 1-fluoroethyl, 1,2-difluoroethyl,3-fluoropropyl, 1-fluoropropyl, 2-fluoropropyl, 4-fluorobutyl,5-fluoroamyl, 6-fluorohexyl, 7-fluoroheptyl, 8-fluorooctyl,2-chloroethyl, 3-chloropropyl, 4-chlorobutyl, 3-bromopropyl,10-fluorodecyl, 12-fluorododecyl, 16-fluorohexadecyl, 18-fluorooctadecyland the like. The alkyl group of 1-4 carbons denoted by R¹² includes,for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl andthe like; and the haloalkyl group of 1-4 carbons includes, for example,trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 1-fluoroethyl,1,2-difluoroethyl, 3-fluoropropyl, 1-fluoropropyl, 2-fluoropropyl,4-fluorobutyl, 2-chloroethyl, 3-chloropropyl, 4-chlorobutyl;3-bromopropyl and the like.

The halogen atom denoted by R¹³ includes, for example, fluorine atom,chlorine atom, bromine atom, and the like; the alkyl group of 1-4carbons includes, for example, methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, tert-butyl and the like; the haloalkyl group of 1-4carbons includes, for example, trifluoromethyl, 2-fluoroethyl,2,2,2-trifluoroethyl, 1-fluoroethyl, 1,2-difluoroethyl, 3-fluoropropyl,1-fluoropropyl, 2-fluoropropyl, 4-fluorobutyl, 2-chloroethyl,3-chloropropyl, 4-chlorobutyl; 3-bromopropyl and the like; the alkoxylgroup of 1-4 carbons includes, for example, methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, isobutyloxy, sec-butyloxy and the like; thehaloalkoxyl group of 1-4 carbons includes, for example, difluoromethoxy,trifluoromethoxy, 2-fluoroethoxy, 2,2,2-trifluoroethoxy,1,1,2,2-tetrafluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy,2,2-dichloro-1,1-difluoroethoxy, 2,2,3,3,3-pentafluoropropyloxy,1,1,1,3,3,3-hexafluoro- 2-propyloxy, 1,1,2,3,3,3-hexafluoropropyloxy,3,3,4,4,4-pentafluoro-2-butyloxy, 3-fluoropropyloxy, 4-fluorobutyloxy,2-chloroethoxy, 3-chloropropoxy, 4-chlobutyloxy, 3-bromopropoxy and thelike; the alkylthio group of 1-4 carbons includes, for example,methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio,isobutylthio, sec-butylthio, tert-butylthio and the like; thehaloalkylthio group of 1-4 carbons includes, for example,fluoromethylthio, difluoromethylthio, trifluoromethylthio,2-fluoroethylthio, 2,2,2-trifluoroethylthio,1,1,2,2-tetrafluoroethylthio, 2-chloro-1,1,2-trifluoroethylthio,2,2-dichloro-1,1-difluoroethylthio, 2,2,3,3,3-pentafluoropropylthio,1,1,1,3,3,3-hexafluoro-2-propylthio, 1,1,2,3,3,3-hexafluoropropylthio,3,3,4,4,4-pentafluoro-2-butylthio, 3-fluoropropylthio,4-fluorobutylthio, 2-chloroethylthio, 3-chloropropylthio,4-chlorobutylthio, 3-bromopropylthio and the like; the alkylsulfinylgroup of 1-4 carbons includes, for example, methylsulfinyl,ethylsulfinyl, n-propylsulfinyl, 2-propylsulfinyl, n-butylsulfinyl,2-butylsulfinyl, 2-methylpropylsulfinyl, 1,1-dimethylethylsulfinyl andthe like; the haloalkylsulfinyl group of 1-4 carbons includes, forexample, fluoromethylsulfinyl, difluoromethylsulfinyl,trifluoromethylsulfinyl, 2-fluoroethylsulfinyl,2,2,2-trifluoroethylsulfinyl, 1,1,2,2-tetrafluoroethylsulfinyl,2-chloro-1,1,2-trifluoroethylsulfinyl,2,2-dichloro-1,1-difluoroethylsulfinyl,2,2,3,3,3-pentafluoropropylsulfinyl,1,1,1,3,3,3-hexafluoro-2-propylsulfinyl,1,1,2,3,3,3-hexafluoropropylsulfinyl,3,3,4,4,4-pentafluoro-2-butylsulfinyl, 3-fluoropropylsulfinyl,4-fluorobutylsulfinyl, 2-chloroethylsulfinyl, 3-chloropropylsulfinyl,4-chlorobutylsulfinyl, 3-bromopropylsulfinyl and the like; thealkylsulfonyl group of 1-4 carbons includes, for example,methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 2-propylsulfonyl,n-butylsulfonyl, 2-butylsulfonyl, 2-methylpropylsulfonyl,1,1-dimenthylethylsulfonyl and the like; the haloalkylsulfonyl group of1-4 carbons includes, for example, fluoromethylsulfonyl,difluoromethylsulfonyl, trifluoromethylsulfonyl, 2-fluoroethylsulfonyl,2,2,2-trifluoroethylsulfonyl, 1,1,2,2-tetrafluoroethylsulfonyl,2-chloro-1,1,2-trifluoroethylsulfonyl,2,2-dichloro-1,1-difluoroethylsulfonyl,2,2,3,3,3-pentafluoropropylsulfonyl,1,1,1,3,3,3-hexafluoro-2-propylsulfonyl,1,1,2,3,3,3-hexafluoropropylsulfonyl,3,3,4,4,4-pentafluoro-2-butylsulfonyl, 3-fluoropropylsulfonyl,4-fluorobutylsulfonyl, 2-chloroethylsulfonyl, 3-chloropropylsulfonyl,4-chlorobutylsulfonyl, 3-bromopropylsulfonyl and the like; thealkylsulfonyloxy group of 1-4 carbons includes, for example,methylsulfonyloxy, ethylsulfonyloxy, 2-propylsulfonyloxy,n-propylsulfonyloxy, n-butylsulfonyloxy and the like; and thehaloalkylsulfonyloxy group of 1-4 carbons includes, for example,chloromethylsulfonyloxy, trifluoromethylsulfonyloxy,difluoromethylsulfonyloxy, 2-chloroethylsulfonyloxy,3-chloropropylsulfonyloxy, 4-chlorobutylsulfonyloxy and the like.

The alkyl group of 1-8 carbons denoted by R¹⁴ or R¹⁵ includes, forexample, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,isobutyl, n-amyl, 1,2-dimethylpropyl, neopentyl, 1-ethylpropyl, n-hexyl,4-methylpentyl, sec-pentyl, n-heptyl, n-octyl and the like; thehaloalkyl group of 1-8 carbons includes, for example, trifluoromethyl,2-fluoroethyl, 2,2,2-trifluoroethyl, 1-fluoroethyl, 1,2-difluoroethyl,3-fluoropropyl, 1-fluoropropyl, 2-fluoropropyl, 4-fluorobutyl,5-fluoroamyl, 6-fluorohexyl, 7-fluoroheptyl, 8-fluorooctyl,2-chloroethyl, 3-chloropropyl, 4-chlorobutyl, 3-bromopropyl and thelike; the alkoxyalkyl group of 3-8 total carbons includes, for example,2-methoxyethyl, ethoxymethyl, 1-methoxyethyl, 2-ethoxyethyl,3-methoxypropyl, 2-methoxypropyl, 2-ethoxypropyl, 4-methoxybutyl,1-methoxypropyl, n-propyloxymethyl, isopropyloxymethyl,3-n-propyloxypropyl, 4-n-propyloxybutyl, 6-ethoxyhexyl, 5-ethoxypentyl,4-ethoxybutyl and the like; the (haloalkoxy)alkyl group of 3-8 totalcarbons includes, for example, 2-(trifluoroethoxy)ethyl,(2-fluoroethoxy)methyl, (2,2,2-trifluoroethoxy)methyl,1-(trifluoromethoxy)-ethyl, 3-(trifluoromethoxy)propyl,2-(trifluoromethoxy)-propyl, 2-(2,2,2-trifluoroethoxy)propyl,4-(difluoromethoxy)butyl, 1-(fluoromethoxy)propyl,(3-fluoropropyloxy)methyl, 4-(3-fluoropropyloxy)butyl,6-(2,2,2-trifluoroethoxy)hexyl, 5-(2-fluoroethoxy)pentyl,4-(2,2-difluoroethoxy)butyl and the like. The alkyl group of 1-8 carbonsdenoted by R¹⁶ includes, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, isobutyl, n-amyl, 1,2-dimethylpropyl,neopentyl, 1-ethylpropyl, n-hexyl, 4-methylpentyl, sec-pentyl, n-heptyl,n-octyl and the like; the haloalkyl group of 1-8 carbons includes, forexample, trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl,1-fluoroethyl, 1,2-difluoroethyl, 3-fluoropropyl, 1-fluoropropyl,2-fluoropropyl, 4-fluorobutyl, 5-fluoroamyl, 6-fluorohexyl,7-fluoroheptyl, 8-fluorooctyl, 2-chloroethyl, 3-chloropropyl,4-chlorobutyl, 3-bromopropyl and the like; the alkoxyalkyl group of 2-8total carbons includes, for example, methoxymethyl, 2-methoxyethyl,ethoxymethyl, 1-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl,2-methoxypropyl, 2-ethoxypropyl, 4-methoxybutyl, 1-methoxypropyl,n-propyloxymethyl, isopropyloxymethyl, 3-n-propyloxypropyl,4-n-propyloxybutyl, 6-ethoxyhexyl, 5-ethoxypentyl, 4-ethoxybutyl and thelike; and the (haloalkoxy)alkyl of 2-8 total carbons includes, forexample, (fluoromethoxy)methyl, 2-(trifluoroethoxy)ethyl,(2-fluoroethoxy)methyl, ( 2,2,2-trifluoroethoxy)methyl,1-(trifluoromethoxy)ethyl, 3-(trifluoromethoxy)propyl,2-(trifluoromethoxy)propyl, 2-(2,2,2-trifluoroethoxy)-propyl,4-(difluoromethoxy)butyl, 1-(fluoromethoxy)-propyl,(3-fluoropropyloxy)methy1,4-(3-fluoropropyloxy)-butyl,6-(2,2,2-trifluoroethoxy)hexyl, 5-(2-fluoroethoxy)pentyl,4-(2,2-difluoroethoxy)butyl and the like.

The alkyl group of 1-18 carbons denoted by R¹⁷ includes, for example,methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, n-amyl, neopentyl, tert-pentyl, 1-methylbutyl, n-hexyl,n-heptyl, n-octyl, 1-methylheptyl, n-dodecyl, n-hexadecyl, n-octadecyland the like; the haloalkyl group of 1-18 carbons includes, for example,trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 1-fluoroethyl,1,2-difluoroethyl, 3-fluoropropyl, 1-fluoropropyl, 2-fluoropropyl,4-fluorobutyl, 5-fluoroamyl, 6-fluorohexyl, 7-fluoroheptyl,8-fluorooctyl, 2-chloroethyl, 3-chloropropyl, 4-chlorobutyl,3-bromopropyl, 10-fluorodecyl, 12-fluorododecyl, 16-fluorohexadecyl,18-fluorooctadecyl and the like; the alkoxyalkyl group of 3-18 totalcarbons includes, for example, methoxymethyl, 2-methoxyethyl,ethoxymethyl, 1-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl,2-methoxypropyl, 2-ethoxypropyl, 4-methoxybutyl, 1-methoxypropyl,n-propyloxymethyl, isopropyloxymethyl, 3-n-propyloxypropyl,4-n-propyloxybutyl, 6-ethoxyhexyl, 5-ethoxypentyl, 4-ethoxybutyl,7-ethoxyheptyl, 8-ethoxyoctyl, 9-ethoxynonyl, 10-ethoxydecyl,11-ethoxyundecyl, 12-ethoxydodecyl, 13-ethoxytridecyl,14-ethoxytetradecyl, 15-ethoxypentadecyl, 16-ethoxyhexadecyl and thelike; the (haloalkoxy)alkyl group of 3-18 total carbons includes, forexample, 2-(trifluoroethoxy)ethyl, (2-fluoroethoxy)methyl,(2,2,2-trifluoroethoxy)methyl, 1-(trifluoromethoxy)ethyl,3-(trifluoromethoxy)propyl, 2-(trifluoromethoxy)propyl,2-(2,2,2-trifluoroethoxy)propyl, 4-(difluoromethoxy)butyl,1-(fluoromethoxy)propyl, (3-fluoropropyloxy)methyl,4-(3-fluoropropyloxy)butyl, 6-(2,2,2-trifluoroethoxy)-hexyl,5-(2-fluoroethoxy)pentyl, 4-(2,2-difluoroethoxy)butyl,5-(1,1,2,2-tetrafluoroethoxy)propyl,6-(2-chloro-1,1,2-trifluoroethoxy)hexyl,7-(2,2-dichloro-1,1-difluoroethoxy)heptyl,8-(2,2,3,3,3-pentafluoropropyloxy)octyl, 8-(2-fluoroethoxy)octyl,9-(1,1,1,3,3,3-hexafluoro-2-propyloxy)nonyl,10-(1,1,2,3,3,3-hexafluoropropyloxy)decyl, 10-(3,3,4,4,4-pentafluoro-2-butyloxy)decyl, 11-(3-fluoropropyloxy)undecyl,11-(4-fluorobutyloxy)undecyl, 10-(6-fluorohexyloxy)decyl,16-(2-chloroethoxy)hexadecyl, 15-(3-chloropropyloxy)-pentadecyl and thelike; the alkoxyhaloalkyl group of 3-18 total carbons includes, forexample, 2,2-difluoro-2-methoxyethyl, 2-fluoro-3-methoxypropyl,2,2-difluoro-3-ethoxypropyl, 4-ethoxy-2,2,3,3-tetrafluorobutyl,5-ethoxy-2,2,3,3,4,4-hexafluoropentyl,6-ethoxy-2,2,3,3,4,4,5,5-octafluorohexyl,4-n-amyloxy-2,2,3,3-tetrafluorobutyl,6-isobutoxy-2,2,3,3,4,4,5,5-octafluorohexyl,2,2,3,3,4,4-hexafluoro-5-n-hexyloxypentyl,4-n-nonyloxy-2,2,3,3-tetrafluorobutyl,5-n-decyloxy-2,2,3,3,4,4-hexafluoropentyl,2,2,3,3,4,4,5,5-octafluoro-n-dodecyloxyhexyl and the like; thealkylthioalkyl group of 3-18 total carbons includes, for example,2-methylthioethyl, 2-ethylthiomethyl, 1-methylthioethyl,2-ethylthioethyl, 3-methylthiopropyl, 2-methylthiopropyl,2-ethylthiopropyl, 4-methylthiobutyl, 1-methylthiopropyl,n-propylthiomethyl, isopropylthiomethyl, 3-n-propylthiopropyl,4-n-propylthiobutyl, 6-ethylthiohexyl, 5-ethylthiopentyl,4-ethylthiobutyl, 7-ethylthioheptyl, 8-ethylthiooctyl, 9-ethylthiononyl,11-methylthioundecyl, 11-ethylthioundecyl, 13-ethylthioundecyl,14-ethylthiotetradecyl, 8-n-heptylthiooctyl, 15-methylthiopentadecyl,15-ethylthiopentadecyl, 17-methylthiooctadecyl and the like; the(haloalkylthio)-alkyl group of 3-18 total carbons include, for example,2-(trifluoroethylthio)ethyl, (2-fluoroethylthio)methyl,(2,2,2-trifluoroethylthio)methyl, 1-(trifluoromethylthio)ethyl,3-(trifluoromethylthio)propyl, 2-(trifluoromethylthio)propyl,2-(2,2,2-trifluoroethylthio)propyl, 4-(difluoromethylthio)butyl,1-(fluoromethylthio)propyl, (3-fluoropropylthio)methyl,4-(3-fluoropropylthio)butyl, 6-(2,2,2-trifluoroethylthio)hexyl,5-(2-fluoroethyl-thio)pentyl, 4-(2,2-difluoroethylthio)butyl,5-(1,1,2,2-tetrafluoroethylthio)propyl,6-(2-chloro-1,1,2-trifluoroethylthio)hexyl,7-(2,2-dichloro-1,1-difluoroethylthio)heptyl,8-(2,2,3,3,3-pentafluoropropylthio)-octyl, 8-(2-fluoroethylthio)octyl,9-(1,1,1,3,3,3-hexafluoro-2-propylthio)nonyl,10-(1,1,2,3,3,3-hexafluoropropylthio)decyl,10-(3,3,4,4,4-pentafluoro-2-butylthio)decyl,11-(3-fluoropropylthio)undecyl, 11-(4-fluorobutylthio)undecyl,10-(6-fluorohexylthio)decyl, 16-(2-chloroethylthio)hexadecyl,15-(3-chloropropylthio)pentadecyl and the like; the cycloalkyl group of3-8 carbons which may be substituted by the alkyl group of 1-10 carbonsincludes, for example, cyclopropyl, 1-methylcyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1-ethylcyclobutyl,2-n-decylcyclopentyl and the like; the cycloalkyl group of 3-8 carbonswhich is substituted by the haloalkyl group of 1-10 carbons includes,for example, 1-trifluoromethylcyclopropyl, 3-(3-fluoropropyl)cyclobutyl,2-(2,2,2-trifluoroethyl)cyclopentyl, 4-(1,2-difluoroethyl)cyclohexyl,3-(2,2,3,3,4,4,4-heptafluorobutyl)cycloheptyl,2-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)cyclooctyland the like; the halocycloalkyl group of 3-8 carbons which may besubstituted by the alkyl group of 1-10 carbons includes, for example,2,2,3,3-tetrafluorocyclopropyl, 2,2,3,3,4,4-hexafluorocyclobutyl,2,2,3,3,4,4,5,5-octafluorocyclopentyl,2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorocyclooctyl,1-methyl-2,2,3,3-tetrafluorocyclopropyl,2-n-nonyl-3,3,4,4,5,5,6,6-octafluorocyclohexyl and the like; thecycloalkyl group of 3-8 carbons which is substituted by the alkoxy groupof 1-10 carbons includes, for example, 1-methoxycyclopropyl,2-ethoxycyclopentyl, 5-n-decylcyclooctyl and the like; and thecycloalkyl group of 3-8 carbons which is substituted by the haloalkoxygroup of 1-10 carbons includes, for example,1-(2,2-difluoroethoxy)cyclopropyl, 2-(2,2,2-trifluoroethoxy)cyclopentyl,4-(8-fluorooctyloxy)-cyclooctyl and the like.

In the present invention, there is preferable an amide compoundrepresented by the formula of ##STR7## wherein R¹ an alkyl group of 1-4carbons or a haloalkyl group of 1-4 carbons; R² and R³ independently area hydrogen atom, a halogen atom, an alkyl group of 1-6 carbons, acycloalkyl group of 3-6 carbons, a haloalkyl group of 1-6 carbons, aphenyl group or an alkoxy group of 1-6 carbons,

R⁴ is a hydrogen atom or an alkyl group of 1-4 carbons

R⁵ and R⁶ independently are a hydrogen atom or an alkyl group of 1-4carbons;

R⁷ is a hydrogen atom, a halogen atom or an alkyl group of 1-4 carbons;

A is the group represented by the formula of ##STR8##

R⁸ is a halogen atom, an alkyl group of 1-8 carbons, a haloalkyl groupof 1-8 carbons, a haloalkoxy group of 1-8 carbon an alkylthio group of1-8 carbons, a haloalkylthio group of 1-8 carbons, an alkenylthio groupof 2-8 carbons, an alkynylthio group of 2-8 carbons, an alkylsulfinylgroup of 1-8 carbons, an alkylsulfonyl group of 1-8 carbons;

R⁹ is a haloalkoxy group of 1-8 carbons, an alkylthio group of 1-8carbons, a haloalkylthio group of 1-8 carbons, an alkenylthio group of2-8 carbons, an alkynylthio group of 2-8 carbons, an alkylsulfinyl groupof 1-8 carbons, an alkylsulfonyl group of 1-8 carbons,

Each R¹⁰ is a halogen atom, an alkyl group of 1-8 carbons, a haloalkylgroup of 1-8 carbons; provided that R⁸ and R¹⁰ may be linked at theirends, when they are adjacent each other, to form a saturatedfive-membered ring which contains 0-2 oxygen atom therein;

X is an oxygen atom or a sulfur atom; Y is an oxygen atom, a sulfuratom, a sulfinyl, sulfonyl or methylene group.

There are more preferably exemplified the following compounds:

N-[4-(4-methylthiophenoxy)benzyl]-1,3-dimethylpyrazole-5-carboxamide;

N-[4-(4-methylthiophenoxy)benzyl]-1,3,4-trimethylpyrazole-5-carboxamide;

N-[4-(4-methylthiophenoxy)benzyl]-1,5-dimethylpyrazole-3-carboxamide;and

N-[4-(4-methylthiophenoxy)benzyl]-4-chloro-1,3-dimethylpyrazole-5-carboxamide.

The substituents in R⁸ and R⁹ are preferably-S-alkyl, morepreferably-SCH₃. The substituent represented by A is preferablysubstituted at 3-position, more preferably at 4-position of the benzenering.

Examples of the insect pests against which the compounds of the presentinvention are efficacious are Lepidoptera including diamondback moth(Plutella xylostella), rice stem borer (Chilo suppressalis), riceleafroller (Cnaphalocrocis medinalis), armyworms (or cutworms), loopers,common cabbageworm (Pieris rapae crucivora), case-making clothes moth(Tinea translucens), webbing clothes moth (Tineola bisselliella) etc.;Diptera including common mosquito (Culex pipiens pallens), Yellow fevermosquito (Aedes aeqypti), Anopheles mosquitos, Aedes mosquitos, housefly(Musca domestica) etc.; Dictyoptera including German cockroach(Blattella germanica), smokybrown cockroach (Periplaneta fuliginosa),brown cockroach (Periplaneta brunnea), American cockroach (Periplanetaamericana) etc.; Coleoptera including adzuki-bean weevil (Callosobruchuschinensis), southern corn rootworm (Diabrotica undecimpunctata),northern corn rootworm (Diabrotica longicornis), scarab beetles etc.;mites such as two-spotted spider mite (Tetranychus urticae), citrus redmite (Panonychus citri) and carmine mite (Tetranychus cinnabarinus);ticks such as ox tick and other animal parastic ticks; room dust acarietc.; Hemiptera including planthoppers such as brown planthopper(Nilaparvata lugens) and smaller brown planthopper (Laodelphaxstriatellus), leafhoppers such as green rice leafhopper (Nephotettixcincticeps), aphids such as green peach aphid (Myzus persicae), stinkbugs, whiteflies etc.; as well as Hymenoptera, Thysanoptera, Orthopteraand the like. The compounds of the present invention are alsoefficacious against insect pests which have been increased in theirresistance to the existing insecticides and acaricides. They furtherexhibit preventive and remedial efficacy against various kinds of plantdiseases.

The following are typical method for producing the present compound, anda proper method can, of course, be selected in accordance with the kindsof the functional groups such as R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ X and Y.

Production Method A: Production of an amide compound [I-1] which isrepresented by the formula [I] but R⁴ is a hydrogen atom or an alkylgroup of 1-4 carbons and X is an oxygen atom.

The amide compound [I-1] is produced by the reaction of a carboxyliccompound represented by the formula [II], ##STR9## wherein V is achlorine atom, a bromine atom, or hydroxy, methoxy, ethoxy, propyloxy or1-imidazolyl group, with an amine compound represented by the formula[III], ##STR10## wherein R⁴ is a hydrogen atom or an alkyl group of 1-4carbons, and Rs, R⁶, R⁷, A and l are the same meanings as defined above.

When V in the formula [II] is a chlorine atom, a bromine atom or1-imidazolyl group, the reaction is carried out in a solvent includingethers such as diethyl ether, tetrahydrofuran and dioxane, aromatichydrocarbons such as toluene, benzene, xylene, chlorobenzene andpyridine, hydrocarbons such as n-hexane, n-heptane and cyclohexane,halogenated hydrocarbons such as methylene chloride, chloroform, carbontetrachloride and 1,2-dichloroethane, esters such as ethyl acetate andmethyl acetate, water, nitriles such as acetonitrile, polar solventssuch as N,N-dimethylformamide, N,N-dimethylacetamide,N-methylpyrrolidone and dimethyl sulfoxide, and mixtures thereof, at atemperature of -20° to 100° C., preferably 0° to 50° C., and normally inthe presence of a base including sodium hydroxide, potassium hydroxide,sodium carbonate, potassium carbonate, triethylamine, pyridine and thelike with a ratio of 1 to 10 moles based on 1 mole of the carboxyliccompound represented by the formula [II].

In case of a two-phase reaction where water is used as the solvent, thereaction rate can be usually accelerated by the use of a phase transfercatalyst including tetra-n-butylammonium bromide, benzyltriethylammoniumchloride and the like.

When V in the formula [II] is hydroxy, methoxy, ethoxy or propyloxygroup, the reaction is carried out either without solvents or in a highboiling solvent including, for example, polar solvents such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone anddimethyl sulfoxide, and aromatic hydrocarbons such as benzene, toluene,xylene and chlorobenzene, at a reaction temperature of 50° to 250° C.

If necessary and appropriate, acidic substances such as sulfuric acid,benzenesulfonic acid, p-toluenesulfonic acid and activated silica gel orbasic substances such as pyridine, triethylamine, sodium ethoxide,sodium methoxide and activated alumina, for example, can be used as areaction catalyst in an amount of 0.0001 to 1 part by weight based on 1part by weight of the carboxylic compound represented by the formula[II].

In general, the amine compound represented by the formula [III] is usedwith a ratio of 0.1 to 10 moles, preferably with a ratio of 0.8 to 1.2mole, based on 1 mole of the carboxylic compound represented by theformula [II]. A reaction period is normally from 5 minutes to 100 hours,preferably from 30 minutes to 10 hours.

Alternatively, when V in the formula [II] is hydroxy group, thefollowing method is also applicable.

Thus, the carboxylic compound of the formula [II] wherein V is hydroxygroup is subjected to a reaction of dehydrating condensation with theamine compound represented by the formula [III] either in the presenceor absence of an innert organic solvent and in the presence of adehydrating agent to produce the subjective present compound. Thedehydrating agent includes, for example, carbodiimides such asdicyclohexylcarbodiimide and1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide, inorganic dehydratingagents such as tetrachlorosilane, and the like The innert organicsolvent includes, for example, aliphatic hydrocarbons such as n-pentane,n-hexane, n-heptane and cyclohexane, aromatic hydrocarbons such asbenzene, toluene, xylene, chlorobenzene, pyridine and o-dichlorobenzene,chlorinated hydrocarbons such as methylene chloride, chloroform, carbontetrachloride, tetrachloroethylene and 1,2-dichloroethane, esters suchas methyl acetate and ethyl acetate, amides such asN,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone,nitriles such as acetonitrile, ethers such as diethyl ether,tetrahydrofuran and dioxane, and the like. The reaction is carried outat a temperature of -20° to 100° C. using the dehydrating agent normallywith a ratio of 0.5 to 10 moles, preferably with a ratio of 1 to 5 molesand using the amine compound represented by the formula [III]normallywith a ratio of 0.1 to 10 moles, preferably with a ratio of 0.8 to 1.2mole, each based on 1 mole of the carboxylic compound represented by theformula [II]. A reaction period is normally from 5 minutes to 100 hours,preferably from 30 minutes to 10 hours.

Production Method B: Production of an amide compound [I-2] which isrepresented by the formula [I] but X is a sulfur atom.

The amide compound [I-2] is produced by the reaction of an amidecompound represented by the formula [I-3], ##STR11## wherein R¹ R², R³,R⁴, R⁵, R⁶, R⁷, A, Y, and l are the same meanings as defined for thecompound [I-2], with phosphorus pentasulfide or a Lawesson's Reagent.

Solvent usable in this method are aromatic hydrocarbons such as benzene,toluene, xylene, monochlorobenzene, pyridine and quinoline, and thelike, or mixtures thereof, and the reaction is carried out using 0.2 to20 moles of phosphorus pentasulfide or 0.5 to 50 moles of the Lawesson'sReagent bassed on 1 mole of the amide compound represented by theformula [I-3], at a temperature of 0° to 250° C., preferably 20° to 150°C., and for a period of 0.5 to 50 hours.

Production method C: Production of an amide compound [I-4] which isrepresented by the formula [I] but R⁴ is an alkyl group of 1-4 carbonsor a group of the formula --S(O)_(m) R¹¹ ; R⁵ and R⁶ independently ofone another are each a hydrogen atom or an alkyl group of 1-4 carbons;and X is an oxygen atom.

The amide compound [I-4] is produced by the reaction of an amidecompound represented by the formula [I-5], ##STR12## wherein R¹ R², R³,R⁴, R⁵, R⁶, R⁷, A, Y and l are the same meanings as defined for thecompound [I-4], with a compound represented by the formula [IV],

    R.sup.4 - D                                                [IV]

wherein R⁴ is an alkyl group of 1-4 carbons, an alkylcarbonyl group of1-8 total carbons or a group of the formula --S(O)_(m) R¹¹ and D isleaving group such as a halogen atom.

Solvents usable in this method are ethers such as diethylether,tetrahydrofuran and dioxane, aroamtic hydrocarbons such as toluene,benzene, xylene, chlorobenzene and pyridine, hydrocarbons such asn-hexane, n-heptane and cyclohexane, halogenated hydrocarbons such asmethylene chloride, chloroform, carbon tetrachloride and1,2-dichloroethane, and the like or mixtures thereof, and the reactionis carried out in the presence of a base.

The base usable here includes, for example, organic bases such astriethylamine, pyridine and N,N-dimethylaminopyridine, alkali metalhydrides such as sodium hydride, and alkyllithium compounds such asn-butyllithium. A molar ratio used is 1 to 10 moles, preferably 1.1 to 2moles, of the compound represented by the formula [IV] based on 1 moleof the amide compound represented by the formula [I-5]. The base is usedwith a ratio of 1 to 5 moles, preferably 1.1 to 2 moles, based on 1 moleof the amide compound represented by the formula [I-5]. A reactiontemperature is -20° to 100° C., preferably 0° to 50° C., and a reactionperiod is from 10 minutes to 50 hours, preferably 1 to 24 hours.

The carboxylic compound represented by the above formula [II] can beprepared by the methods disclosed in, for example, Bull. Soc. Chim. Fr.,293 (1966), Khim. Farm. Zh., 4, 19 (1970), Org. Synth., IV, 351 (1963),Ann., 250, 257 (1889), Chem. Ber., 109, 268 (1976), Ann. Chim. (Rome),55, 576 (1965), Chem. Ber., 112, 1712 (1979), Chem. Ber., 107, 1318(1974), Chem. Ber., 109, 253 (1976), Aust. J. Chem., 36, 135 (1983),EP-A-27020 (1981), DE-A-2728523 (1979) and the like or by the analogousmethods thereto.

The amine compound represented by the formula [III] can be prepeared,for example, by the methods shown below.

Preparation Method a: Preparation of an amine compound [III-1] which isrepresented by the formula [III] but R⁴, R⁵ and R⁶ are each a hydrogenatom; R⁸ (in A) is a halogen atom, an alkyl group of 1-8 carbons, ahaloalkyl group of 1-8 carbons, a haloalkoxy group of 1-8 carbons, analkylthio group of 1-8 carbons, a haloalkylthio group of 1-8 carbons; R⁹is an alkylthio group of 1-8 carbons or a haloalkylthio group of 1-8carbons, provided that R⁸ and R¹⁰ may be linked at their ends, when theyare adjacent each other, to form a saturated five-membered ring whichcontains 0-2 oxygen atom therein; and Y is an oxygen atom, a sulfur atomor a methylene group.

The amine compound [III-1] is prepared by reducing a nitrile compoundrepresented by the formula [V], ##STR13## wherein R⁷, A, Y, and l arethe same meanings as defined for the compound [III1].

The reducing reaction applicable here includes, for example, a methodusing a reducing agent such as lithium aluminum hydride,borane-tetrahydrofuran complex or sodium borohydride-sulfur, andcatalytic hydrogenation using a catalyst such as platinum [IV] oxide,rhodium-aluminum oxide or Raney nickel, each disclosed in e.g. J. Amer.Chem. Soc., 70, 3788 (1948), J. Amer. Chem. Soc., 82, 681 (1960), Can.J. Chem., 49, 2990 (1971), J. Org. Chem., 37, 335 (1972), J. Amer. Chem.Soc., 82, 2386 (1960), Org. Synth., III, 229 (1955) or the like, and theanlogous methods thereto.

Among the amine compounds [III-1], those represented by the formula[III-2] are novel: ##STR14## wherein A is the group represented by theformula of ##STR15## R⁸ and R⁹ independently of one an other are each analkylthio group of 1-8carbons or a haloalkylthio group of 1-8 carbons;R⁷ and R¹⁰ independently of one another are each a hydrogen atom, ahalogen atom or methyl group; Y is an oxygen atom, a sulfur atom ormethylene group; and l is the same meanings as defined above.

The above reaction is carried out in a solvent including ethers such asdiethyl ether, tetrahydrofuran, dioxane and 1,2-dimethoxyethane,aromatic hydrocarbons such as toluene, benzene and xylene, hydrocarbonssuch as n-hexane, n-heptane and cyclohexane, and mixtures thereof, at atemperature of -20° and 200° C., preferably 0° to 150° C., and using areducing agent including metal hydrogen complex compounds such aslithium aluminum hydride, aluminum hydride, sodium aluminum hydride,lithium trimethoxyaluminum hydride, sodium triethoxyaluminum hydride andsodium borohydride-sulfur, and borane compounds such asborane-tetrahydrofuran complex, normally with a ratio of 1 to 10equivalents based on 1 mole of the nitrile compound represented by theformula [V]. A reaction period is normally from 5 minutes to 00 hours,preferably from 30 minutes to 10 hours.

Alternatively, when the reducing reaction is carried out by thecatalytic hydrogenation, the following method is also applicable.

Thus, the nitrile compound represented by the formula [V] is subjectedto the catalytic hydrogenation in a solvent including alcohols such asmethanol and ethanol, esters such as ethyl acetate, and mixturesthereof, in the presence of a catalyst and under the condition of 1 to 5atm in a hydrogen gas atmosphere to obtain the amine compound [III-1].The catalyst usable here includes platinum [IV] oxide, Raney nickel,rhodium-aluminum oxide and the like. The catalyst is normally used in anamount of 0.0001 to 1 part by weight based on 1 part by weight of thenitrile compound represented by the formula [V]. A reaction temperatureis 0° to 150° C., and a reaction period is normally from 10 minutes to100 hours, preferably from 30 minutes to 10 hours.

Preparation Method b: Preparation of an amine compound [III-3] which isrepresented by the formula [III] but R⁴ is a hydrogen atom or an alkylgroup of 1-4 carbons; R⁵ is a hydrogen atom; R⁸ is a halogen atom, analkyl group of 1-8 carbons, a haloalkyl group of 1-8 carbons, acycloalkyl group of 3-8 total carbons, an alkoxy group of 1-8 carbons, ahaloalkoxy group of 1-8 carbons, a haloalkoxy group of 1-8 carbons, analkylthio group of 1-8 carbons, a haloalkylthio group of 1-8 carbons, R⁶is a halogen atom, a haloalkyl group of 1-8 carbons, a haloalkoxy groupof 1-8 carbons, an alkylthio group of 1-8 carbons, a haloalkylthio groupof 1-8 carbons, provided that R⁸ and R¹⁰ may be linked at their ends,when they are adjacent each other, to form a saturated five- memberdring which contains 0-2 oxygen atom therein, provided that two of R¹⁰ Smay be the same or different from each other: and Y is an oxygen atom, asulfur atom or methylene group.

The amine compound [III-3] is prepared by the reductive condensation ofa carbonyl compound represented by the formula [VI], ##STR16## whereinR⁶, R⁷, A, Y, and l are the same meanings as defined for the compound[III-3], with an amine compound represented by the formula [VII],

    R.sup.4 --NH.sub.2                                         [VII]

wherein R⁴ is a hydrogen atom or an alkyl group of 1-4 carbons.

This reaction is carried out in the manner disclosed in, for example,Org. React., 4, 174 (1948), J. Amer. Chem. Soc., 61, 3566 (1939), J.Amer. Chem. Soc., 93, 2897 (1971), Org. React., 5, 323 (1949), and thelike, or by the anlogous methods thereto.

Among the amine compounds [III-3], those represented by the formula[III-4] are novel: ##STR17## wherein A is the group represented by theformula of ##STR18## R⁴ and R⁶ independently of one another are each ahydrogen atom or an alkyl group of 1-4 carbons; R⁸ and R⁹ independentlyof one another are each an alkylthio group of 1-8 carbons or ahaloalkylthio group of 1-8 carbons; R⁷ and R¹⁰ independently of oneanother are each a hydrogen atom, a halogen atom or methyl group,provided that two of R¹⁰ s may be the same or different from each other;Y is an oxygen atom, a sulfur atom or methylene group; and l is the samemeanings as defined above.

The reductive condensation reaction between the carbonyl compoundrepresented by the formula [VI] and the amine compound represented bythe formula [VII] proceeds through an intermediate imine compoundrepresented by the formula [VIII], ##STR19## wherein R⁴, R⁶, R⁷, thegroup A, Y, and l are the same meanings as defined for the compound[III-3]. This intermediate may be directly led to the amine compound[III-3] by continuing the reductive reaction without separation. If theimine compound represented by te formula [VIII] is intended forseparation, a dehydrating condensation reaction is conducted inaccordance with the usual manner. Thus, the reaction is carried outeither without solvents or in a solvent including, for example, water,alcohols such as methanol and ethanol, aromatic hydrocarbons such asbenzene, toluene and pyridine, ethers such as diethyl ether andtetrahydrofuran, halogenated hydrocarbons such as methylene chloride andchloroform, aliphatic hydrocarbons such as n-hexane and cyclohexane, andmixtures thereof, in the presence or absence of a base such as sodiumhydroxide, potassium hydroxide, potassium carbonate and sodium carbonateor an acidic compound such as sulfuric acid, hdyrochloric acid andp-toluenesulfonic acid, using normally 1 to 100 moles of the aminecompound represented by the formula [VII] based on 1 mole of thecarbonyl compound represented by the formula [VI], at a reactiontemperature of -20° to 150° C., preferably 0° to 120° C., and for areaction period of from 5 minutes to 20 hours.

In preparing the amine compound [III-3] by the reduction of the iminecompound represented by the formula [VIII], a reducing agent usableincludes, for example, sodium borohydride, lithium aluminum hydride,sodium cyanoborohydride, lithium cyanoborohydride,borane-tetrahydrofuran complex and the like, and is normally used in anamount of 1 to 100 equivalents based on 1 mole of the imine compoundrepresented by the formula [VIII]. Though a solvent used in thisreaction should be selected depending on the kind of reducing agents, itincludes, in general, water, alcohols such as methanol and ethanol,ethers such as diethyl ether and tetrahydrofuran, and the like ormixtures thereof. A reaction temperature is normally -10° to 50° C., anda reaction period is 0.5 to 50 hours.

On the other hand, when the amine compound [III-3] is prepared from thecarbonyl compound represented by the formula [VI] and the amine compoundrepresented by the formula [VII] without separating the imine compoundrepresented by the formula [VIII], the preparation can be performed byincorporating a reducing agent in the reaction system. The reducingagent usable here includes, for example, sodium borohydride, sodiumcyanoborohydride, lithium cyanoborohydride and the like. In general,based on 1 mole of the carbonyl compound represented by the formula[VI], the reducing agent is used in an amount of 1 to 100 equivalents,and the amine compound represented by the formula [VII] is used in anamount of 1 to 50 moles. A solvent usable includes water, alcohols suchas methanol and ethanol, ethers such as dioxane and tetrahydrofuran, andthe like or mixtures therreof. a reaction temperature is -10° to 150°C., and a reaction period is 0.5 to 50 hours.

When catalytic hydrogenation is applied to the reduction of the iminecompound produced in the reaction system, the amine compound [III-3] canbe prepared by subjecting the carbonyl compound represented by theformula [VI] to the reaction with the same amine compound used in theaforementioned preparation under the condition of 1 to 100 atm in ahydrogen gas atmosphere and using a catalyst. Raney nickel, platinum,platinum(IV) oxide, palladium black or the like can be used as thecatalyst with a ratio of 0.0001 to 0.1 part by weight based on 1 part byweight of the carbonyl compound represented by the formula [VI]. Areaction temperature is 50° to 200° C., preferably 80° to 180° C., and areaction period is 1 to 24 hours, preferably 2 to 12 hours.

Alternatively, the reduction of the imine compound produced in thereaction system can also be conducted by using formic acid, in which thecarbonyl compound represented by the formula [VI] and either a formamidecompound or a formate of an amine compound are subjected to a reactiontogether with formic acid. A reaction temperature is 100° to 250° C.,preferably 120° to 200° C., and a reaction period is 1 to 50 hours,preferably 5 to 24 hours. Examples of the formamide compound usableherein are formamide, N-monoalkyl substituted formamides of 2-5 totalcarbons including N-methylformamide, and the like, and examples of theformate of an amine compound are ammonium formate, monoalkylamineformates of 2-5 total carbons including ethylammonium formate, and thelike. The formamide or formate compound is used in an amount of 3 to 10moles, preferably 4 to 6 moles, based on 1 mole of the carbonyl compoundrepresented by the formula [VI]. Formic acid is used in an amount of0.01 to 1 part by weight, preferably 0.05 to 0.1 part by weight based on1 part by weight of the carbonyl compound represented by the formula[VI]. Further, the N-formyl derivative produced here can be hydrolyzedin the usual manner to obtain the amine compound [III-3].

Preparation Method c: Prepation of an amine compound [III-5] which isrepresented by the formula [III] but R⁴ is a hydrogen atom; R⁵ and R⁶independently of one another are each a hydrogen atom or an alkyl groupof 1-4 carbons; R⁸ is a halogen atom, an alkyl group of 1-8 carbons, ahaloalkyl group of 1-8 carbons, a haloalkoxy group of 1-8 carbons, analkylthio group of 1-8 carbons, a haloalkylthio group of 1-8 carbons, analkenylthio group of 2-8 carbons, a haloalkenylthio group of 2-8carbons, an alkynylthio group of 2-8 carbons, an alkylsulfinyl group of1-8 carbons, an alkylsulfonyl group of 1-8 carbons, R¹⁰ is a haloalkylgroup of 1-8 carbons, a haloalkoxy group of 1-8 carbons, an alkylthiogroup of 1-3 carbons, a haloalkylthio group of 1-3 carbons, analkenylthio group of 2- 6 carbons, a haloalkenylthio group of 2-6carbons, an alkynylthio group of 2-6 carbons, an alkylsulfinyl group of1-3 carbons, an alkylsulfonyl group of 1-3 carbons, provided that two ofR¹⁰ s may be the same or different from each other, provided that R⁸ andR¹⁰ may be linked at their ends, when they are adjacent each other, toform a saturated five-membered ring which contains 0-2 oxygen atomtherein; Y is an oxygen atom, a sulfur atom, sulfoxide, sulfonyl,methylene.

The amine compound [III-5] is prepared by subjecting a carboxyliccompound represented by the formula [IX], ##STR20## wherein R⁵, R⁶, R⁷,A, Y, and l are the same meanings as defined for the compound [III-5],and U is amino or hydroxy group, or a chlorine atom, to a rearrangementreaction, for example, Hofmann reaction, Curtius rearrangement, Lossenrearrangement, Schmidt rearrangement of the like to obtain an isocyanatecompound represented by the formula [X], ##STR21## wherein R⁵, R⁶, R⁷,A, Y, and l are the same meanings as defined for the compound [III-5],then hydrolyzing the product, with or without separation.

The rearrangement reaction is carried out in the manner disclosed in,for example, Org. React. 3, 267 (1946), Org. React, 3, 337 (1946), Chem.Rev., 33, 209 (1943), Org. React, 3, 307 (1946), J. Amer. Chem. Soc.,71, 3352 (1949), J. Amer, Chem. Soc., 82, 2857 (1960), and the like, orby the analogous methods thereto.

Among the amine compounds [III-5], those represented by the formula[III-6] are novel; ##STR22## wherein A is the group represented by theformula of ##STR23## R⁸ or R⁹ is an alkylthio group of 1-8 carbons orhaloalkylthio group of 1-8 carbons; R⁷ and R¹⁰ independently of oneanother are each a hydrogen atom, a halogen atom or methyl group,provided that two of R¹⁰ s may be the same or different from each other;and R⁵, R⁶, Y, and l are the same meanings as defined for the compound[III-5].

When U in the crboxylic compound represented by the formula [IX] is achlorine atom, for example, Curtius rearrangement is applied, and theamine compound [III-5] is prepared, in general, by heating thecarboxylic compound [XI] together with 1 to 20 equivalents of sodiumazide based on 1 mole of the carboxylic compound represented by theformula [IX] in a solvent including aromatic hydrocarbons such asbenzene, toluene and xylene, halogenated hydrocarbons, such as methylenechloride, chloroform and 1,2-dichloroethane, ethers such as diethylether and tetrahydrofuran, water and the like or mixtures thereof, thenheating the resulting isocyanate compound represented by the formula [X]together with a mineral acid such as concentrated hydrochloric acid oran aqueous solution containing a base such as sodium hydroxide. Areaction temperature is 20° to 200° C., and a reaction period is 0.5 to100 hours.

Preparation Method d: Preparation of an amine compound [III-7] which isrepresented by the formula [III] but R⁴ is a hydrogen atom or an alkylgroup of 1-4 carbons, and R⁵ is a hydrogen atom.

The amine compound [III-7] is prepared by the reaction of a halogenatedcompound represented by the formula [XI], ##STR24## wherein R⁶, R⁷, A,Y, and l are the same meanings as defined for the compound [III-7], andT is a halogen atom, with an amine compound represented by the formula[VII].

This method is carried out normally in a solvent including alcohols suchas methanol, ethanol and isopropanol, ethers such as diethyl ether,tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene,benzene, xylene and chlorobenzene, hydrocarbons such as n-hexane,n-heptane and cyclohexane, water, nitriles such as acetonitrile, polarsolvents such as N,N-dimethylformamide, N,N-dimethylacetamide,N-methylpyrrolidone and dimethyl sulfoxide, and mixtures thereof, at atemperature of -20° to 100° C., preferably 0° to 50° C., and using theamine compound represented by the formula [VII] with a ratio of usually1 to 100 moles, preperably 10 to 50 moles, based on 1 mole of thehalogenated compound represented by the formula [XI]. A reaction periodis 1 to 200 hours, preferably 10 to 100 hours. The amine compoundrepresented by the formula [VII] may be subjected to the reaction in theform of a gaseous state, an aqueous solution or an alcoholic solutionsuch as a methanol solution.

In order to prepare the amine compound [III-7] with higher yields, thefollowing method is exemplified.

Thus, the halogenated compound represented by the formula [XI] isallowed to react with an alkali metal salt of cyclic imide including,for example, potassium succinimide, potassium phthalimide and sodium2,3-diphenylmaleimide, in a solvent including ethers such as diethylether, tetrahydrofuran and dioxane, aromatic hydrocrbons such astoluene, benzene, xylene, chlorobenzene and pyridine, hydrocarbons suchas n-hexane, n-heptane and cyclohexane, esters such as ethyl acetate andmethyl acetate, nitriles such as acetonitrile, polar solvents such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrrolidone anddimethyl sulfoxide, and mixtures thereof, at a temperature of -20° to100° C., preferably 0° to 50° C., using the alkali metal salt of cyclicimides usually with a ratio of 1 to 10 moles based on 1 mole of thehalogenated compound represented by the formula [XI]. A reaction periodis normally 1 to 100 hours, preferably 5 to 24 hours. The resultingN-substituted cyclic imide can then be subjected to a hydrolysis byeither mineral acids such as hydrochloric acid or alkali metalhydroxides such as sodium hydroxide, or to a hydrazinolysis to obtainthe amine compound [III-7]. A reaction solvent usable here includesalcohols such as methanol, ethanol and isopropanol, water, ethers suchas diethyl ether, tetrahydrofuran and dioxane, and aromatic hydrocarbonssuch as toluene, benzene, xylene and chlorobenzen. The hydrolysis bymeans of the mineral acid as a catalyst is conducted using 0.0001 to 1part by weight of the mineral acid based on 1 part by weight of theN-substituted cyclic imide, while the hydrolysis by means of the alkalimetal hydroxide is conducted using 1 to 10 moles of the alkali metalhydroxide based on 1 mole of the N-substituted cyclic imide, and thehydrazinolysis is conductd using 1 to 10 moles of hydrazine based on 1mole of the N-substituted cyclic imide. A reaction temperature is 0° to140° C., preferalby 50° to 100° C., and a reaction period is 1 to 100hours, preferably 2 to 24 hours.

Preparation Method e: Preparation of an amine compound [III-8] which isrepresented by te formula [III] but R⁴ is a hydrogen atom, and R⁵ is acyano group.

The amine compound [III-8] is prepared by subjecting a carbonyl compoundrepresented by the formula [XII], ##STR25## wherein R⁶, R⁷, A, Y and lare the same meanings as defined for the compound [III-8], to thereactions with ammonia and subsequently with hydrogen cyanide.

Among the amine compounds [III-8], those represented by the formula[III-9] are novel: ##STR26## wherein A is the group represented by theformula of ##STR27## R⁶ is a hydrogen atom or an alkyl group of 1-4carbons; R⁸ and R⁹ independently of one another are each an alkylthiogroup of 1-8 carbons or a haloalkylthio group of 1-8 carbons; R⁷ and R¹⁰independently of one another are each a hydrogen atom, a halogen atom ormethyl group, provided that two of R¹⁰ s may be the same or differentfrom each other; Y is an oxygen atom, a sulfur atom, sulfinyl, sulfonylor methylene group; and l is the same meanings as defined above.

Examples of a reaction solvent usable in this reaction are water and anymixtures of water and an organic solvent miscible with water includingwater/methanol, water/ethanol, water/tetrahydrofuran and the like. Areaction temperature is -10° to 60° C., preferably 0° to 40° C. Areaction period is 1 to 24 hours, preferably 2 to 10 hours. Ammonia andhydrogen cyanide are used each with a ratio of 1 to 10 moles, preferably1.1 to 2 moles, based on 1 mole of the carbonyl compound represented bythe formula [XII]. Combinations of ammonium halides such as ammoniumchloride and alkali cyanides such as sodium cyanide are also applicablein place of the combination of ammonia and hydrogen cyanide.

The aforementioned compounds represented by the formulas [V], [VI],[IX], [XI] and [XII] can be prepared in the usual manner or by theanalogoous methods thereto.

A diphenyl ether compound represented by the formula [XIII], ##STR28##wherein A is the group represented by the formula of ##STR29## R⁷ andR¹⁰ independently of one another are each a hydrogen atom, a halogenatom or methyl, provided that two of R¹⁰ s may be the same or differentfrom each other; R⁸ and R⁹ independently of one another are each analkylthio group of 1-8 carbons or a haloalkylthio group of 1-8 carbons;l is the same meanings as defined above; and E is cyano group or a grouprepresented by the formula ##STR30## in which R⁶ is the same meaning asdefined above, R⁵ is merely a hydrogen atom or an alkyl group of 1-4carbons among those defined for the formula [I], R¹⁸, R¹⁹, R²⁰ and R²¹independently of one another are each a lower alkyl group, but R¹⁸ andR¹⁹ may be linked at their ends to form a saturated five- orsix-membered ring, is novel and is prepared, for example, in accordancewith the following manner.

Preparation Method f: The diphenyl ether compound represented by theformula [XIII] is prepared in the presence of a base by the reaction ofa compound represented by the formula [XIV], ##STR31## wherein E, R⁷ andl are the same meanings as defined in the formula [XIII], and L¹ is ahalogen atom or hydroxy group, with a compound represented by theformula [XV],

    L.sup.2 --A                                                [XV]

wherein A is the same meanings as defined in the formula [XIII], and L²is a halogen atom or hydroxy group, provided that when L¹ in the formula[XIV] is a halogen atom, L² in the formula [XV] is hydroxy group, andwhen L¹ is hydroxy group, L² is a halogen atom.

This reaction is carried out either without solvents or in a solventincluding aromatic hydrocarbons such as toluene, benzene, xylene andpyridine, polar solvents such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylpyrrolidone, hexamethyl phosphorictriamide and dimethyl sulfoxide, and mixtures thereof, using 0.5 to 10moles, preferably 0.8 to 2 moles, of the halobenzene compound based on 1mole of the phenolic compound. A reaction temperature is 50° to 250° C.,preferably 70° to 200° C., and a reaction period is 1 to 50 hours,preferably 2 to 24 hours. It is possible to use metallic copper orcuprous compounds such as copper(I) chloride and copper(I) iodide in anamount of 0.0001 to 0.1 part by weight based on 1 part by weight of thephenolic compound represented by the formula [XIV] or XV].

A carbonyl compound represented by the formula XIII-1] is novel and isprepared from an acetal compound represented by the formula [XIII-2],##STR32## wherein R⁶, R⁷, R¹⁸, R¹⁹, l and A are the same meanings asdefined in the formula [XIII].

The acetal compound represented by the formula [XIII-2] is subjected toa reaction in a solvent including ethers such as diethyl ether,tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene,benzene, xylene and chlorobenzene, hydrocarbons such as n-hexane,n-heptane and cyclohexane, halogenated hydrocarbons such as methylenechloride, chloroform, carbon tetrachloride and 1,2-dichloroethane,aliphatic ketones such as acetone and methyl ethyl ketone, water andmixtures thereof, under an acidic catalyst to obtain the carbonylcompound represented by the formula [XIII-1]. The acidic catalystincludes mineral acids such as hydrochloric acid and sulfuric acid,organic acids such as acetic acid, trifluoroacetic acid andp-toluenesulfonic acid, clay minerals such as montmorillonite, andmixtures thereof, and it can be used in an amount of 0.0001 to 0.1 partby weight, preferably 0.001 to 0.01 part by weight, based on 1 part byweight of the acetal compound represented by the formula [XIII-2]. Areaction temperature is 0° to 150° C., preferably 20° to 100° C., and areaction period is from 10 minutes to 10 hours, preferably 1 to 5 hours.

Further, a carboxylic compound represented by the formula [XVI] is noveland can be prepared from a carboxylic acid represented by the formula[XVII], ##STR33## wherein R⁵, R⁶, R⁷, l and A are the same meanings asdefined in the formula [XIII].

This reaction is carried out by subjecting the carboxylic acidrepresented by the formula [XVII] to a reaction with a halogenationagent either in a solvent or without solvents, in which the solventincludes ethers such as diethyl ether, tetrahydrofuran and dioxane,aromatic hydrocarbons such as toluene, benzene, xylene andchlorobenzene, hydrocarbons such as n-hexane, n-heptane and cyclohexane,halogenated hydrocarbons such as methylene chloride, chloroform, carbontetrachloride and 1,2-dichloroethane, and mixtures tehreof. Thehalogenation agent includes phosphoryl chloride, thionyl chloride,phosphorus pentachloride, phosphorus trichloride, phosgene and the like,and it can be used with a ratio of 1 to 10 moles, preferably 1.1 to 5moles, based on 1 mole of the carboxylic acid represented by the formula[XVII]. In order to accelerate the reaction, it is possible to use acatalyst such as zinc chloride, pyridine, iodine and triethylamine in anamount of 0.00001 to 0.01 part by weight, preferably 0.0001 to 0.001part by weight, based on 1 part by weight of the carboxylic acidrepresented by the formula [ XVII]. A reaction temperature is 0° to 200°C., preferably 50° to 150° C., and a reaction period is 1 to 100 hours,preferably 2 to 50 hours.

The carboxylic acid represented by the formula [XVII] is novel and canbe prepard from an ester compound represented by the formula [XIII-3],##STR34## wherein R⁵, R⁶, R⁷, R²⁰, l and A are the same meanings asdefined in the formula [XIII].

The ester compound represented by the formula [XIII-3] is hydrolyzed ina solvent including ethers such as diethyl ether, tetrahydrofuran anddioxane, aromatic hydrocarbons such as toluene, benzene, xylene andchlorobenzene, hydrocarbons such as n-hexane, n-heptane and cyclohexane,halogenated hydrocarbons such as methylene chloride, chloroform, carbontetrachloride and 1,2-dicloroethane, water and mixtures thereof, in thecoexistence of water and an acidic catalyst or a base to form thecarboxylic acid [XVII]. The acidic catalyst includes mineral acids suchas hydrochloric acid and sulfuric acid, while the base includes alkalihydroxides such as sodium hydroxide and potassium hydroxide, and alkalimetal salts of weak acid such as potassium carbonate. When the acidiccatalyst is applied, it can be used in an amount of 0.0001 to 0.1 partby weight, preferably 0.001 to 0.01 part by weight, based on 1 part byweight of the ester compound represented by the formula [XIII-3] Whenthe base is applied, it can be used with a ratio of 1 to 10 moles,preferably 1.1 to 2 moles, based on 1 mole of the ester compoundrepresented by the formula [XIII-3]. A reaction temperature is 0° to150° C., preferably 20° to 80° C., and a reaction period is 1 to 100hours, preferably 2 t 24 hours.

An alcoholic compound represented by the formula [XVIII] is novel andcan be prepared from the ester compound represented by the formula[XIII-3], ##STR35## wherein R⁷, R²⁰, l and A are the same meanings asdefined in the formula [XIII].

This reaction is performed by reducing the ester compound represented bythe formula [XIII-3] in a solvent including ethers such as diethylether, tetrahydrofuran and dioxane, aromatic hydrocarbons such astoluene, benzene, xylene and chlorobenzene, and mixtures thereof. Areducing agent applicable here includes metal hydrogen complex compoundssuch as lithium aluminum hydride, lithium borohydride, aluminum hydrideand lithium trimethoxyaluminum hydride, and it can be used with a ratioof 1 to 10 equivalents, preferably 1 to 2 equivalents, based on 1 moleof the ester compound represented by the formula [XIII-3]. A reactiontemperature is -10° to 100° C., preferably 0° to 70° C., and a reactionperiod is from 10 minutes to 50 hours, preferably from 30 minutes to 24hours.

A halogenated compound represented by the formula [XIX] is novel and canbe prepared from an alcoholic compound represented by the formula[XVIII-1], ##STR36## wherein R⁶, R⁷, l and A are the same meanings asdefined in the formula [XIII], and T is the same meanings as defined inthe formula [XI].

The alcoholic compound [XVIII-1] is subjected to a reaction with ahalogenation agent either in a solvent or without solvents, in which thesolvent includes ethers such as diethyl ether, tetrahydrofuran anddioxane, aromatic hydrocarbons such as toluene, benzene, xylene andchlorobenzene, hydrocarbons such as n-hexane, n-heptane and cyclohexane,halogenated hydrocarbons such as methylene chloride, chloroform, carbontetrachloride and 1,2-dichloroethane, and mixtures thereof. Thehalogenation agent includes phosphoryl chloride, thionyl chloride,phosphorus pentachloride, phosphorus trichloride, phosgene and the like,and it can be used with a ratio of 1 to 50 moles, preferably 1.1 to 5moles, based on 1 mole of the alcoholic compound represented by theformula [XVIII-1]. A reaction temperature is 0° to 200° C., preferably50° to 150° C., and a reaction period is 1 to 100 hours, preferable 2 to50 hours.

The alcoholic compound represented by the formula [XVIII-1] can beprepared from the carbonyl compound represented by the formula [XIII-1],##STR37## wherein R⁶, R⁷, l and A are the same meanings as defined inthe formula [XIII].

This reaction is performed by reducing the carbonyl compound representedby the formula [XIII-1] in a solvent including ethers such as diethylether, tetrahydrofuran and dioxane, aromatic hydrocarbons such astoluene, benzene, xylene and chlorobenzene, and mixtures thereof. Areducing agent applicable here includes metal hydrogen complex compoundssuch as lithium aluminum hydride, lithium borohydride, aluminum hydrideand lithium trimethoxyaluminum hydride, and it can be used with a ratioof 1 to 10 equivalents, preferably 1 to 2 equivalents, based on 1 moleof the carbonyl compound represented by the formula [XIII-1]. A reactiontemperature is -10° to 100° C., preferably 0° to 70° C., and a reactionperiod is from 10 minutes to 50 hours, preferably from 30 minutes to 24hours. The present compound can be obtained as a final product byconducting a usual aftertreatment subsequently to the completion of thereaction.

The present compounds have optical isomers originated from R⁵ and R⁶,and include also the mixtures of any isomers, each of which can be usedas the active ingredient of insecticidall and/or acaricidal composition.

The compounds of the present invention are specifically shown in thefollowing Table 1to 5. However, these compounds are merely forexemplification, and not for limitation.

                                      TABLE 1                                     __________________________________________________________________________     ##STR38##                                                                    Compound                                                                      No.   R.sup.1                                                                          R.sup.2                                                                           R.sup.3                                                                          X R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         (R.sup.7)l                                                                        Y  R.sup.8                                        __________________________________________________________________________    1-1   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              CH.sub.3                                       1-2   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              C.sub.2 H.sub.5                                1-3   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              n-C.sub.3 H.sub.7                              1-4   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              i-C.sub.3 H.sub.7                              1-5   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              n-C.sub.4 H.sub.9                              1-6   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              i-C.sub.4 H.sub.9                              1-7   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              sec-C.sub.4 H.sub.9                            1-8   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              n-C.sub.5 H.sub.11                             1-9   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              i-C.sub.5 H.sub.11                             1-10  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              sec-C.sub.5 H.sub.11                           1-11  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              neo-C.sub.5 H.sub.11                           1-12  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              n-C.sub.6 H.sub.13                             1-13  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              n-C.sub.7 H.sub.15                             1-14  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              n-C.sub.8 H.sub.17                             1-15  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              CF.sub.2 H                                     1-16  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              CF.sub.3                                       1-17  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              Cl                                             1-18  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              F                                              1-19  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              Br                                             1-20  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              OCF.sub.2 H                                    1-21  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              OCF.sub.3                                      1-22  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              OCBrF.sub.2                                    1-23  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              OCF.sub.2 CF.sub.2 H                           1-24  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              OCH.sub.2 CF.sub.3                             1-25  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              OCF.sub.2 CClFH                                1-26  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              OCH.sub.2 CH.sub.2 F                           1-27  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              SCH.sub.3                                      1-28  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              SC.sub.2 H.sub.5                               1-29  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S-n-C.sub.3 H.sub.7                            1-30  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S-i-C.sub.3 H.sub.7                            1-31  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S-n-C.sub.4 H.sub.9                            1-32  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S-i-C.sub.4 H.sub.9                            1-33  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S-sec-C.sub.4 H.sub.9                          1-34  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S-n-C.sub.5 H.sub.11                           1-35  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              SCF.sub.2 H                                    1-36  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              SCF.sub.3                                      1-37  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              SCH.sub.2 CH.sub.2 F                           1-38  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              SCH.sub.2 CF.sub.3                             1-39  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              SCF.sub.2 CF.sub.2 H                           1-40  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              SCF.sub.2 CClFH                                1-41  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              SCF.sub.2 CFHCF.sub.3                          1-42  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              SCH.sub.2 CF.sub.2 CF.sub.3                    1-43  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              SCH.sub.2 CF.sub. 2 CF.sub.2 CF.sub.3          1-44  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              SCH.sub.2 CHCH.sub.2                           1-45  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              SCH.sub.2 CH                                   1-46  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              SCH.sub.2 CHCHCCH                              1-47  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S(O)CH.sub.3                                   1-48  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S(O)C.sub.2 H.sub.5                            1-49  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S(O)CF.sub.2 H                                 1-50  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S(O)CF.sub.3                                   1-51  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S(O)CF.sub.2 CF.sub.2 H                        1-52  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S(O)CH.sub.2 CF.sub.3                          1-53  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S(O).sub.2 CH.sub.3                            1-54  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S(O).sub.2 C.sub.2 H.sub.5                     1-55  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S(O).sub.2 CF.sub.2 H                          1-56  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S(O).sub.2 CF.sub.3                            1-57  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S(O).sub.2 CH.sub.2 CF.sub.3                   1-58  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-O                                                                              S(O).sub.2 CF.sub.2 CF.sub.2 H                 1-59  CH.sub.3                                                                         3-CH.sub.3                                                                        4-Cl                                                                             O H H H H   4-S                                                                              Cl                                             1-60  CH.sub.3                                                                         3-CH.sub.3                                                                        4-Cl                                                                             O H H H H   4-O                                                                              CH.sub.3                                       1-61  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H   4-S                                                                              CH.sub.3                                       1-62  CH.sub.3                                                                         3-CH.sub.3                                                                        4-Cl                                                                             O H H H H   4-O                                                                              SCH.sub.3                                      1-63  CH.sub.3                                                                         3-CH.sub.3                                                                        4-Cl                                                                             O H H H H   4-O                                                                              SC.sub.2 H.sub.5                               1-64  CH.sub.3                                                                         3-CH.sub.3                                                                        4-Cl                                                                             O H H H H   4-O                                                                              CH.sub.3                                       1-65  CH.sub.3                                                                         3-CH.sub.3                                                                        4-Cl                                                                             O H H H H   4-O                                                                              C.sub.2 H.sub.5                                __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR39##                                                                    Compound                                                                      No.   R.sup.1                                                                            R.sup.2                                                                              R.sup.3                                                                             X R.sup.4                                                                          R.sup.5                                                                           R.sup.6                                                                          (R.sup.7)l                                                                        Y  R.sup.9                            __________________________________________________________________________    2-1   CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              OCF.sub.2 H                        2-2   CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              OCBrF.sub.2                        2-3   CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              OCF.sub.2 CF.sub.2 H               2-4   CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              OCF.sub.2 CF.sub.2 H               2-5   CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              OCH.sub.2 CF.sub.3                 2-6   CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              OCF.sub.2 CClFH                    2-7   CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              OCF.sub.2 CCl.sub.2 H              2-8   CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              OCF.sub.2 CFHCF.sub.3              2-9   CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              OCH.sub.2 CH.sub.2 F               2-10  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCH.sub.3                          2-11  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SC.sub.2 H.sub.5                   2-12  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S-n-C.sub.3 H.sub.7                2-13  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S-i-C.sub.3 H.sub.7                2-14  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S-n-C.sub.4 H.sub.9                2-15  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S-i-C.sub.4 H.sub.9                2-16  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S-sec-C.sub.4 H.sub.9              2-17  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S-n-C.sub.5 H.sub.11               2-18  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                               ##STR40##                         2-19  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                               ##STR41##                         2-20  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                               ##STR42##                         2-21  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCH.sub.2 CH.sub.2 CH(CH.sub.3)                                               .sub.2                             2-22  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCH.sub.2 C(CH.sub.3).sub.3        2-23  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S-tert-C.sub.4 H.sub.9             2-24  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S-n-C.sub.6 H.sub.13               2-25  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S-n-C.sub.7 H.sub.15               2-26  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S-n-C.sub.8 H.sub.17               2-27  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCH.sub.2(CF.sub.2).sub.3CF.sub                                               .3                                 2-28  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCF.sub.3                          2-29  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCH.sub.2 CH.sub.2 F               2-30  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCH.sub.2 CF.sub.3                 2-31  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCF.sub.2 CF.sub.2 H               2-32  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCF.sub.2 CClFH                    2-33  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCF.sub.2 CCl.sub.2 H              2-34  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCF.sub.2 CFHCF.sub.3              2-35  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCF.sub.2 CFHCF.sub.2 CF.sub.3                                                .                                  2-36  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCH.sub.2 CF.sub.2 CF.sub.3        2-37  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCH.sub.2 CF.sub.2 CF.sub.2                                                   CF.sub.3                           2-38  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCH.sub.2 CHCH.sub.2               2-39  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                               ##STR43##                         2-40  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                               ##STR44##                         2-41  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCH.sub.2 CHCHCH.sub.3             2-42  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCH.sub.2 CCH                      2-43  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                               ##STR45##                         2-44  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCH.sub.2 CCCH.sub.3               2-45  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCH.sub.2 CHCHCCH                  2-46  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S(O)CH.sub.3                       2-47  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S(O)C.sub.2 H.sub.5                2-48  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S(O)-n-C.sub.3 H.sub.7             2-49  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S(O)-n-C.sub.4 H.sub.9             2-50  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S(O)-i-C.sub.3 H.sub.7             2-51  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S(O).sub.2 CH.sub.3                2-52  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              S(O).sub.2 C.sub.2 H.sub.5         2-53  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   3-O                                                                              SCH.sub.3                          2-54  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   3-O                                                                              SC.sub.2 H.sub.5                   2-55  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  2-F 4-O                                                                              4-SCH.sub.3                        2-56  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  2-F 4-O                                                                              4-SC.sub.2 H.sub.5                 2-57  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  2-F 4-O                                                                              4-SCF.sub.2 H                      2-58  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  2,5-F.sub.2                                                                       4-O                                                                              4-SCH.sub.3                        2-59  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  3-CH.sub.3                                                                        4-O                                                                              4-SCH.sub.3                        2-60  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  CH.sub.3                                                                          H  H   4-O                                                                              4-SCH.sub.3                        2-61  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  C.sub.2 H.sub.5                                                                   H  H   4-O                                                                              4-SCH.sub.3                        2-62  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  i-C.sub.3 H.sub.7                                                                 H  H   4-O                                                                              4-SCH.sub.3                        2-63  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  CN  H  H   4-O                                                                              SC.sub.2 H.sub.5                   2-64  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  CH.sub.3                                                                          CH.sub.3                                                                         H   4-O                                                                              SCH.sub.3                          2-65  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O CH.sub.3                                                                         H   H  H   4-O                                                                              SCH.sub.3                          2-66  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O C.sub.2 H.sub.5                                                                  H   H  H   4-O                                                                              SCH.sub.3                          2-67  CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   S H  H   H  H   4-O                                                                              SCH.sub.3                          2-68  CH.sub.3                                                                           3-C.sub.2 H.sub.5                                                                    4-H   O H  H   H  H   4-O                                                                              4-SCH.sub.3                        2-69  CH.sub.3                                                                           3-i-C.sub.3 H.sub.7                                                                  4-H   O H  H   H  H   4-O                                                                              SCH.sub.3                          2-70  CH.sub.3                                                                            ##STR46##                                                                           4-H   O H  H   H  H   4-O                                                                              SCH.sub.3                          2-71  CH.sub.3                                                                            ##STR47##                                                                           H     O H  H   H  H   4-O                                                                              SCH.sub.3                          2-72  CH.sub.3                                                                            ##STR48##                                                                           H     O H  H   H  H   4-O                                                                              OCF.sub.2 CF.sub.2 H               2-73  C.sub.2 H.sub.5                                                                    3-CH.sub.3                                                                           H     O H  H   H  H   4-O                                                                              SCH.sub.3                          2-74  i-C.sub.3 H.sub.7                                                                  3-CH.sub.3                                                                           H     O H  H   H  H   4-O                                                                              SCH.sub.3                          2-75                                                                                 ##STR49##                                                                         3-CH.sub.3                                                                           H     O H  H   H  H   4-O                                                                              SCH.sub.3                          2-76  CF.sub.3 CH.sub.2                                                                  3-CH.sub.3                                                                           H     O H  H   H  H   4-O                                                                              SCH.sub.3                          2-77  CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              SCH.sub.3                          2-78  CH.sub.3                                                                           3-CH.sub.3                                                                           4-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              SCH.sub.3                          2-79  CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              OCF.sub.2 CF.sub.2 H               2-80  CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              OCF.sub.2 CF.sub.2 H               2-81  CH.sub.3                                                                           3-CH.sub.3                                                                           4-Br  O H  H   H  H   4-O                                                                              OCF.sub.2 CF.sub.2 H               2-82  CH.sub.3                                                                           3-CH.sub.3                                                                           4-Br  O H  H   H  H   4-O                                                                              SCH.sub.3                          2-83  CH.sub.3                                                                           3-CH.sub.3                                                                           4-C.sub.2 H.sub.5                                                                   O H  H   H  H   4-O                                                                              OCF.sub.2 CF.sub.2 H               2-84  CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              S(O)CH.sub.3                       2-85  CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              S(O).sub. 2 CH.sub.3               2-86  CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O CH.sub.3                                                                         H   H  H   4-O                                                                              4-OCF.sub.2 CF.sub.2 H             2-87  CH.sub.3                                                                           4-Cl   5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              4-OCF.sub.2 CF.sub.2 H             2-88  CH.sub.3                                                                           4-H    5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              SCH.sub.3                          2-89  CH.sub.3                                                                           4-H    5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              SC.sub.2 H.sub.5                   2-90  CH.sub.3                                                                           4-H    5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              SCF.sub.2 CCl.sub.2 H              2-91  CH.sub.3                                                                           4-H    5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              SCH.sub.2 CF.sub.3                 2-92  CH.sub.3                                                                           4-H    5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              SCF.sub.2 CF.sub.2 H               2-93  CH.sub.3                                                                           4-H    5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              S-n-C.sub.3 H.sub.7                2-94  CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              OCF.sub.2 CCl.sub.2 H              2-95  CH.sub.3                                                                           3-OC.sub.2 H.sub.5                                                                   4-H   O H  H   H  H   4-O                                                                              SC.sub.2 H.sub.5                   2-96  CH.sub.3                                                                           3-O-i-C.sub.3 H.sub.7                                                                4-H   O H  H   H  H   4-O                                                                              SC.sub.2 H.sub.5                   2-97  CH.sub.3                                                                           3-OCH.sub.3                                                                          4-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              SCH.sub. 3                         2-98  CH.sub.3                                                                           3-CH.sub.3                                                                           4-Br  O H  H   H  H   4-O                                                                              SCH.sub.3                          2-99  CH.sub.3                                                                           3-CH.sub.3                                                                           5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              OCF.sub.2 CF.sub.2 H               2-100 CH.sub.3                                                                           3-CH.sub.3                                                                           5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              SCH.sub.3                          2-101 CH.sub.3                                                                           3-CH.sub.3                                                                           5-Cl  O H  H   H  H   4-O                                                                              OCF.sub.2 CF.sub.2 H               2-102 CH.sub.3                                                                           3-CH.sub.3                                                                           5-Cl  O H  H   H  H   4-O                                                                              SCH.sub.3                          2-103 CH.sub.3                                                                           4-H    5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              OCF.sub.2 CF.sub.2 H               2-104 CH.sub.3                                                                           4-Br   5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              OCF.sub.2 CF.sub.2 H               2-105 CH.sub.3                                                                           4-Cl   5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              OCF.sub.2 CF.sub.2 H               2-106 CH.sub.3                                                                           3-CH.sub.3                                                                           5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              OCF.sub.2 CF.sub.2 H               2-107 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              SC.sub.2 H.sub.5                   2-108 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              SCF.sub.2 H                        2-109 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              SCF.sub.3                          2-110 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              OCF.sub.3                          2-111 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              S-n-C.sub.3 H.sub.7                2-112 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              S-n-C.sub.4 H.sub.9                2-113 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              S-i-C.sub.3 H.sub.7                2-114 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Br  O H  H   H  H   4-O                                                                              SC.sub.2 H.sub.5                   2-115 CH.sub.3                                                                           3-CH.sub.3                                                                           4-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              SC.sub.2 H.sub.5                   2-116 CH.sub.3                                                                           4-H    5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              SCF.sub.2 H                        2-117 CH.sub.3                                                                           4-H    5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              SCF.sub.3                          2-118 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              SCF.sub.2 H                        2-119 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              SCF.sub.3                          2-120 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  H   H  H   4-O                                                                              OCF.sub.3                          2-121 CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              SCF.sub.2 H                        2-122 CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  H   H  H   4-O                                                                              OCF.sub.3                          2-123 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O CH.sub.3                                                                         H   H  H   4-O                                                                              SCH.sub.3                          2-124 CH.sub.3                                                                           4-CH.sub.3                                                                           5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              SCH.sub.3                          2-125 CH.sub.3                                                                           4-Cl   5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              SCH.sub.3                          2-126 CH.sub.3                                                                           4-Br   5-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              4-SCH.sub.3                        2-127 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  CN  H  H   4-O                                                                              4-SCH.sub.3                        2-128 CH.sub.3                                                                           4-H    5-CH.sub.3                                                                          O H  CN  H  H   4-O                                                                              4-SCH.sub.3                        2-129 CH.sub.3                                                                           3-CH.sub.3                                                                           4-H   O H  CN  H  H   4-O                                                                              4-SCH.sub.3                        2-130 CH.sub.3                                                                           4-Cl   5-CH.sub.3                                                                          O H  CN  H  H   4-O                                                                              4-SCH.sub.3                        2-131 CH.sub.3                                                                           3-OCH.sub.3                                                                          4-H   O H  H   H  H   4-O                                                                              4-SCH.sub.3                        2-132 CH.sub.3                                                                           4-H    5-OCH.sub.3                                                                         O H  H   H  H   4-O                                                                              4-SCH.sub.3                        2-133 CH.sub.3                                                                           3-OC.sub.2 H.sub.5                                                                   4-H   O H  H   H  H   4-O                                                                              4-SCH.sub.3                        2-134 CH.sub.3                                                                           4-H    5-OC.sub.2 H.sub.5                                                                  O H  H   H  H   4-O                                                                              4-SCH.sub.3                        2-135 CH.sub.3                                                                           3-O-i-C.sub.3 H.sub.7                                                                4-H   O H  H   H  H   4-O                                                                              SCH.sub.3                          2-136 CH.sub.3                                                                           4-H    5-O-i-C.sub.3 H.sub.7                                                               O H  H   H  H   4-O                                                                              SCH.sub.3                          2-137 CH.sub.3                                                                           4-Cl   5-OCH.sub. 3                                                                        O H  H   H  H   4-O                                                                              SCH.sub.3                          2-138 CH.sub.3                                                                           3-OCH.sub.3                                                                          4-Br  O H  H   H  H   4-O                                                                              SCH.sub.3                          2-139 CH.sub.3                                                                           4-CH.sub.3                                                                           5-OCH.sub.3                                                                         O H  H   H  H   4-O                                                                              SCH.sub.3                          2-140 CH.sub.3                                                                           3-OCH.sub.3                                                                          4-CH.sub.3                                                                          O H  H   H  H   4-O                                                                              SCH.sub.3                          2-141 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Cl  O H  CH.sub.3                                                                          H  H   4-O                                                                              SCH.sub.3                          2-142 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Br  O H  CH.sub.3                                                                          H  H   4-O                                                                              SCH.sub.3                          2-143 CH.sub.3                                                                           4-H    5-CH.sub.3                                                                          O H  CH.sub.3                                                                          H  H   4-O                                                                              SCH.sub.3                          2-144 CH.sub.3                                                                           3-OCH.sub.3                                                                          4-H   O H  CH.sub.3                                                                          H  H   4-O                                                                              SCH.sub.3                          2-145 CH.sub.3                                                                           3-OCH.sub.3                                                                          4-Br  O H  CH.sub.3                                                                          H  H   4-O                                                                              SCH.sub.3                          2-146 CH.sub.3                                                                           3-CH.sub.3                                                                           4-Br  O H  C.sub.2 H.sub.5                                                                   H  H   4-O                                                                              SCH.sub.3                          2-147 CH.sub.3                                                                           3-OCH.sub.3                                                                          4-H   O H  C.sub.2 H.sub.5                                                                   H  H   4-O                                                                              SCH.sub.3                          2-148 CH.sub.3                                                                           3-OCH.sub.3                                                                          4-Br  O H  C.sub.2 H.sub.5                                                                   H  H   4-O                                                                              SCH.sub.3                          2-149 CH.sub.3                                                                           4-H    5-CH.sub.3                                                                          O H  C.sub.2 H.sub.5                                                                   H  H   4-O                                                                              SCH.sub.3                          2-150 CH.sub.3                                                                           3-CH.sub. 3                                                                          4-Cl  O H  C.sub.2 H.sub.5                                                                   H  H   4-O                                                                              SCH.sub.3                          2-151 CH.sub.3                                                                           3-C.sub.2 H.sub.5                                                                    4-Cl  O H  H   H  H   4-S                                                                              SCH.sub.3                          2-152 CH.sub.3                                                                           3-C.sub.2 H.sub.5                                                                    4-Cl  S H  H   H  H   4-O                                                                              SCH.sub.3                          2-153 CH.sub.3                                                                           3-C.sub.2 H.sub.5                                                                    4-Cl  O H  CH.sub.3                                                                          H  H   4-O                                                                              SC.sub.2 H.sub.5                   2-154 CH.sub.3                                                                           3-C.sub.2 H.sub.5                                                                    4-Cl  O H  CN  H  H   4-O                                                                              SC.sub.2 H.sub.5                   2-155 CH.sub.3                                                                           3-C.sub.2 H.sub.5                                                                    4-Cl  O H  i-C.sub.3 H.sub.7                                                                 H  H   4-O                                                                              SC.sub.2 H.sub.5                   __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________     ##STR50##                                                                    Compound                                                                      No.   R.sup.1                                                                          R.sup.2                                                                            R.sup.3                                                                           X R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         (R.sup.7)λ                                                                 Y  R.sup.8     R.sup.10                         __________________________________________________________________________    3-1   CH.sub.3                                                                         3-CH.sub.3                                                                         4-Br                                                                              O H H H H   4-O                                                                              SCH.sub.3   Cl                               3-2   CH.sub.3                                                                         4-H  5-CH.sub.3                                                                        O H H H H   4-O                                                                              SCH.sub.3   Cl                               3-3   CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H   4-O                                                                              SC.sub.2 H.sub.5                                                                          Cl                               3-4   CH.sub.3                                                                         3-OCH.sub.3                                                                        4-H O H H H H   4-O                                                                              SC.sub.2 H.sub.5                                                                          Cl                               3-5   CH.sub.3                                                                         3-C.sub.2 H.sub.5                                                                  4-Cl                                                                              O H H H H   4-O                                                                              SCH.sub.3   Cl                               3-6   CH.sub.3                                                                         3-OCH.sub.3                                                                        4-H O H H H H   4-O                                                                              CH.sub.3    Cl                               3-7   CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H   4-O                                                                              Cl          C.sub.2 H.sub.5                  3-8   CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H   4-O                                                                              4-OCH.sub.3 OCH.sub.3                        3-9   CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H   4-O                                                                              4-OC.sub.2 H.sub.5                                                                        OCH.sub.3                        3-10  CH.sub.3                                                                         4-H  5-CH.sub.3                                                                        O H H H H   4-O                                                                              CH.sub.3    Cl                               3-11  CH.sub.3                                                                         3-CH.sub.3                                                                         4-Br                                                                              O H H H H   4-O                                                                              CH.sub.3    Cl                               3-12  CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H   4-O                                                                              C.sub.2 H.sub.5                                                                           Cl                               3-13  CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H   4-O                                                                              OC.sub.2 H.sub.5                                                                          Cl                               3-14  CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H   4-O                                                                              CH.sub.3    Cl                               3-15  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   3-O                                                                              SCH.sub.3   Cl                               3-16  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SC.sub.2 H.sub.5                                                                          Cl                               3-17  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SC.sub.2 H.sub.5                                                                          Br                               3-18  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCF.sub.2 H F                                3-19  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCF.sub.2 H Cl                               3-20  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCF.sub.2 H Br                               3-21  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCF.sub.3   Cl                               3-22  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCF.sub.3   Br                               3-23  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCF.sub.2 CF.sub.2 H                                                                      Cl                               3-24  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCF.sub.2 CF.sub.2 H                                                                      F                                3-25  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCF.sub.2 CF.sub.2 H                                                                      Br                               3-26  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.2 CF.sub.3                                                                        Cl                               3-27  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.2 CF.sub.3                                                                        Br                               3-28  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.2 CH.sub.2 F                                                                      Cl                               3-29  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.2 CH.sub.2 F                                                                      F                                3-30  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.3   CH.sub.3                         3-31  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SC.sub.2 H.sub.5                                                                          CH.sub.3                         3-32  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCF.sub.2 H CH.sub.3                         3-33  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.2 CH.sub.2 F                                                                      CH.sub.3                         3-34  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCF.sub.3   CH.sub.3                         3-35  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCF.sub.2 CF.sub.2 H                                                                      CH.sub.3                         3-36  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              OCF.sub.2 CF.sub.2 H                                                                      CH.sub.3                         3-37  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              OCH.sub.2 CF.sub.3                                                                        CH.sub.3                         3-38  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              OCH.sub.2 CH.sub.2 F                                                                      CH.sub.3                         3-39  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              OCF.sub.3   Cl                               3-40  CH.sub.3                                                                         3-CH.sub. 3                                                                        4-H O H H H H   4-O                                                                              OCH.sub.2 CF.sub.3                                                                        Cl                               3-41  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              F           Cl                               3-42  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              Br          CH.sub.3                         3-43  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              Br          Br                               3-44  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              4-Br        CH.sub.3                         3-45  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              4-F         CH.sub.3                         3-46  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              4-CH.sub.3  Cl                               3-47  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              4-C.sub.2 H.sub.5                                                                         Cl                               3-48  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              4-CH.sub.3  Br                               3-49  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              4-C.sub.2 H.sub.5                                                                         Br                               3-50  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              CH.sub.3    F                                3-51  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              C.sub.2 H.sub.5                                                                           F                                3-52  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              Cl          CH.sub.3                         3-53  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              S(O)CH.sub.3                                                                              F                                3-54  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              S(O)C.sub.2 H.sub.5                                                                       Cl                               3-55  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              S(O)C.sub.2 H.sub.5                                                                       Br                               3-56  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              S(O)C.sub.2 H.sub.5                                                                       F                                3-57  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.3   C.sub.2 H.sub.5                  3-58  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                  3-59  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCF.sub.2 H C.sub.2 H.sub.5                  3-60  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.2 CF.sub.3                                                                        C.sub.2 H.sub.5                  3-61  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCF.sub.2 CF.sub.2 H                                                                      C.sub.2 H.sub.5                  3-62  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.2 CF.sub.3                                                                        CH.sub.3                         3-63  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.3   F                                3-64  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.3   Cl                               3-65  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.3   Br                               3-66  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SC.sub.2 H.sub.5                                                                          F                                3-67  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              CH.sub.3    CH.sub.3                         3-68  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              C.sub.2 H.sub.5                                                                           CH.sub.3                         3-69  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              CH.sub.3    Cl                               3-70  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              Cl          Cl                               3-71  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              4-F         Cl                               3-72  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              CH.sub.3    F                                3-73  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              CH.sub.3    Br                               3-74  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.3   C.sub.2 H.sub.5                  3-75  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.3   CH.sub.3                         3-76  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.3   F                                3-77  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.3   OCH.sub.3                        3-78  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              SCH.sub.3   Cl                               3-79  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H 2-F 4-O                                                                              SCH.sub.3   Cl                               3-80  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H S H H H H   4-O                                                                              SCH.sub.3   Cl                               3-81  CH.sub.3                                                                         3-C.sub.2 H.sub.5                                                                  4-H O H H H H   4-O                                                                              SCH.sub.3   Cl                               3-82  CH.sub.3                                                                         3-C.sub.2 H.sub.5                                                                  4-H O H H H H   4-O                                                                              SCH.sub.3   Br                               3-83  CH.sub.3                                                                         4-H  5-CH.sub.3                                                                        O H H H H   4-O                                                                              SC.sub.2 H.sub.5                                                                          Cl                               3-84  CH.sub.3                                                                         4-H  5-CH.sub.3                                                                        O H H H H   4-O                                                                              SC.sub.2 H.sub.5                                                                          Br                               3-85  CH.sub.3                                                                         4-H  5-CH.sub.3                                                                        O H H H H   4-O                                                                              SC.sub.2 H.sub.5                                                                          F                                3-86  CH.sub.3                                                                         3-OCH.sub.3                                                                        4-H O H H H H   4-O                                                                              SCH.sub.3   Cl                               3-87  CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H   4-O                                                                              Cl          CH.sub.3                         3-88  CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H   4-O                                                                              (OCH.sub.2 O)                                3-89  CH.sub.3                                                                         4-H  5-CH.sub.3                                                                        O H H H H   4-O                                                                              CH.sub.3    Cl                               3-90  CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H   4-O                                                                              SCH.sub.3   Br                               3-91  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              (CH.sub.2 CH.sub.2 CH.sub.2 )                3-92  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H   4-O                                                                              (CH.sub.2 OCH.sub.2 )                        3-93  CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H   4-O                                                                              CH.sub.3    CH.sub.3                         3-94  CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H   4-O                                                                              (CH.sub.2 CH.sub.2 CH.sub.2 )                __________________________________________________________________________

                  TABLE 4                                                         ______________________________________                                         ##STR51##                                                                    ______________________________________                                    

wherein the numbers 2 and 3 are to represent the positions ofsubstitution.

    __________________________________________________________________________    Compound                                                                      No.   R.sup.1                                                                          R.sup.2                                                                           R.sup.3                                                                          X R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         (R.sup.7)l                                                                       Y  R.sup.8 R.sup.10                                __________________________________________________________________________    4-1   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              Cl      2,3-(CH.sub.3).sub.2                    4-2   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              CH.sub.3                                                                              2-CH.sub.3 -3-Cl                        4-3   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              Br      2,3-(CH.sub.3).sub.2                    4-4   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              C.sub.2 H.sub.5                                                                       2,3-(CH.sub.3).sub.2                    4-5   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              n-C.sub.3 H.sub.7                                                                     2,3-(CH.sub.3).sub.2                    4-6   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              n-C.sub.4 Hhd 9                                                                       2,3-(CH.sub.3).sub.2                    4-7   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              n-C.sub.5 H.sub.11                                                                    2,3-(CH.sub.3).sub.2                    4-8   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              C.sub.2 H.sub.5                                                                       2-CH.sub.3 -3-Cl                        4-9   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              n-C.sub.3 H.sub.7                                                                     2-CH.sub.3 -3-Cl                        4-10  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                    2,3-(CH.sub.3).sub.2                    4-11  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              Br      2,3-Br.sub.2                            4-12  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              Cl      2,3-Cl.sub.2                            4-13  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              S(O)CH.sub.3                                                                          2,3-Cl.sub.2                            4-14  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCH.sub.3                                                                             2,3-(CH.sub.3).sub.2                    4-15  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SC.sub.2 H.sub.5                                                                      2,3-(CH.sub.3).sub.2                    4-16  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCF.sub.2 H                                                                           2,3-(CH.sub.3).sub.2                    4-17  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCH.sub.2 CF.sub.3                                                                    2,3-(CH.sub.3).sub.2                    4-18  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCH.sub.3                                                                             2,3-(CH.sub.3).sub.2                    4-19  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCH.sub.2 CH.sub.2 F                                                                  2,3-(CH.sub.3).sub.2                    4-20  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCF.sub.2 CF.sub.2 H                                                                  2,3-(CH.sub.3).sub.2                    4-21  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCH.sub.2 CF.sub.3                                                                    2,3-Cl.sub.2                            4-22  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCH.sub.2 CH.sub.2 F                                                                  2,3-Cl.sub.2                            4-23  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCH.sub.3                                                                             2,3-Cl.sub.2                            4-24  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SC.sub.2 H.sub.5                                                                      2,3-Cl.sub.2                            4-25  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCF.sub.2 H                                                                           2,3-Cl.sub.2                            4-26  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCF.sub.2 CF.sub.2 H                                                                  2,3-Cl.sub.2                            4-27  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              CH.sub.3                                                                              2,3-(CH.sub.3).sub.2                    __________________________________________________________________________

                  TABLE 5                                                         ______________________________________                                         ##STR52##                                                                    ______________________________________                                    

wherein the numbers 3 and 5 are to represent the positions ofsubstitution.

    __________________________________________________________________________    Compound                                                                      No.   R.sup.1                                                                          R.sup.2                                                                           R.sup.3                                                                          X R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         (R.sup.7)l                                                                       Y  R.sup.8                                                                             R.sup.10                                  __________________________________________________________________________    5-1   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              Br    3,5-(CH.sub.3).sub.2                      5-2   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              Cl    3,5-(CH.sub.3).sub.2                      5-3   CH.sub.3                                                                         3-CH.sub.3                                                                        4-Cl                                                                             O H H H H  4-O                                                                              Cl    3,5-(CH.sub.3).sub.2                      5-4   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCF.sub.2 H                                                                         3,5-(CH.sub.3).sub.2                      5-5   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCH.sub.2 CF.sub.3                                                                  3,5-(CH.sub.3).sub.2                      5-6   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCF.sub.2 CF.sub.2 H                                                                3,5-(CH.sub.3).sub.2                      5-7   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              CH.sub.3                                                                            3,5-Cl.sub.2                              5-8   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              CH.sub.3                                                                            3,5-Br.sub.2                              5-9   CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              C.sub.2 H.sub.5                                                                     3,5-Cl.sub.2                              5-10  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              Cl    3,5-(CH.sub.3).sub.2                      5-11  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              Br    3,5-(CH.sub.3).sub.2                      5-12  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SCH.sub.3                                                                           3,5-(CH.sub.3).sub.2                      5-13  CH.sub.3                                                                         3-CH.sub.3                                                                        4-H                                                                              O H H H H  4-O                                                                              SC.sub.2 H.sub.5                                                                    3,5-(CH.sub.3).sub.2                      5-14  CH.sub.3                                                                         3-CH.sub.3                                                                        4-Cl                                                                             O H H H H  4-O                                                                              SCH.sub.3                                                                           3,5-(CH.sub.3).sub.2                      __________________________________________________________________________

                  TABLE 6                                                         ______________________________________                                         ##STR53##                                                                    ______________________________________                                    

wherein the numbers 2 and 5 are to represent the positions ofsubstitution.

    __________________________________________________________________________    Compound                                                                      No.   R.sup.1                                                                          R.sup.2                                                                            R.sup.3                                                                           X R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         (R.sup.7)l                                                                       Y  R.sup.8                                                                             R.sup.10                                __________________________________________________________________________    6-1   CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              S(O)C.sub.2 H.sub.5                                                                 2,5-Cl.sub.2                            6-2   CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              S(O)C.sub.2 H.sub.5                                                                 2,5-(CH.sub.3).sub.2                    6-3   CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              S(O)C.sub.2 H.sub.5                                                                 2-Cl-5-CH.sub.3                         6-4   CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              S(O)C.sub.2 H.sub.5                                                                 2-CH.sub.3 -5-Cl                        6-5   CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              S(O)C.sub.2 H.sub.5                                                                 2-F-5-CH.sub.3                          6-6   CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              S(O)C.sub.2 H.sub.5                                                                 2-CH.sub.3 -5-F                         6-7   CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H  4-O                                                                              SCH.sub.3                                                                           2,5-Cl.sub.2                            6-8   CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H  4-O                                                                              SCH.sub.3                                                                           2,5-(CH.sub.3).sub.2                    6-9   CH.sub.3                                                                         3-OCH.sub.3                                                                        4-H O H H H H  4-O                                                                              SCH.sub.3                                                                           2,5-Cl.sub.2                            6-10  CH.sub.3                                                                         4-H  5-CH.sub.3                                                                        O H H H H  4-O                                                                              SCH.sub.3                                                                           2,5-Cl.sub.2                            6-11  CH.sub.3                                                                         4-H  5-CH.sub.3                                                                        O H H H H  4-O                                                                              SCH.sub.3                                                                           2-CH.sub.3 -5-Cl                        6-12  CH.sub.3                                                                         3-C.sub.2 H.sub.5                                                                  4-H O H H H H  4-O                                                                              SCH.sub.3                                                                           2,5-Cl.sub.2                            6-13  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  3-O                                                                              SCH.sub.3                                                                           2,5-Cl.sub.2                            6-14  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCH.sub.3                                                                           2,5-Cl.sub.2                            6-15  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCH.sub.3                                                                           2-Cl-5-CH.sub.3                         6-16  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCH.sub.3                                                                           2-CH.sub.3 -5-Cl                        6-17  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCH.sub.3                                                                           2-F-5-CH.sub.3                          6-18  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCH.sub.3                                                                           2-CH.sub.3 -5-F                         6-19  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SC.sub.2 H.sub.5                                                                    2,5-Cl.sub.2                            6-20  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SC.sub.2 H.sub.5                                                                    2-Cl-5-CH.sub.3                         6-21  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SC.sub.2 H.sub.5                                                                    2-CH.sub.3 -5-Cl                        6-22  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SC.sub.2 H.sub.5                                                                    2-F-5-CH.sub.3                          6-23  CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H  4-O                                                                              CH.sub.3                                                                            2,5-(CH.sub.3).sub.2                    6-24  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SC.sub.2 H.sub.5                                                                    2-CH.sub.3 5-F                          6-25  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCF.sub.2 H                                                                         2,5-Cl.sub.2                            6-26  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCF.sub.2 H                                                                         2-Cl-5-CH.sub.3                         6-27  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCH.sub.2 H                                                                         2-CH.sub.3 -5-F                         6-28  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCF.sub.2 H                                                                         2-F-5-CH.sub.3                          6-29  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCF.sub.2 CF.sub.2 H                                                                2,5-Cl.sub.2                            6-30  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCF.sub.2 CF.sub.2 H                                                                2,5-Cl.sub.2                            6-31  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCF.sub.2 CF.sub.2 H                                                                2-CH.sub.3 -5-Cl                        6-32  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCH.sub.2 CF.sub.3                                                                  2,5-Cl.sub.2                            6-33  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCH.sub.2 CF.sub.3                                                                  2-Cl-5-CH.sub.3                         6-34  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCH.sub.2 CF.sub.3                                                                  2-CH.sub.3 -5-Cl                        6-35  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCH.sub.2 CH.sub.2 F                                                                2,5-Cl.sub.2                            6-36  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCH.sub.2 CH.sub.2 F                                                                2-Cl-5-CH.sub.3                         6-37  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              S(O)CH.sub.3                                                                        2,5-Cl.sub.2                            6-38  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              S(O)CH.sub.3                                                                        2-Cl-5-CH.sub.3                         6-39  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              S(O)CH.sub.3                                                                        2-F-5-CH.sub.3                          6-40  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              S(O)CH.sub.3                                                                        2-CH.sub.3 -5-Cl                        6-41  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              S(O)CH.sub.3                                                                        2-CH.sub.3 -5-F                         6-42  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              C.sub.2 H.sub.5                                                                     2,5-Cl.sub.2                            6-43  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              Cl    2,5-Cl.sub.2                            6-44  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              Br    2,5-Br.sub.2                            6-45  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCH.sub.3                                                                           2,5-(CH.sub.3).sub.2                    6-46  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SC.sub.2 H.sub.5                                                                    2,5-(CH.sub.3).sub.2                    6-47  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCF.sub.2 H                                                                         2,5-(CH.sub.3).sub.2                    6-48  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCH.sub.2 CF.sub.3                                                                  2,5-(CH.sub.3).sub.2                    6-49  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              SCF.sub.2 CF.sub.2 H                                                                2,5-(CH.sub.3).sub.2                    6-50  CH.sub.3                                                                         3-CH.sub.3                                                                         4-Cl                                                                              O H H H H  4-O                                                                              CH.sub.3                                                                            2,5-(CH.sub.3).sub.2                    6-51  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              CH.sub.3                                                                            2-Cl-5-CH.sub.3                         6-52  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              CH.sub.3                                                                            2,5-Cl.sub.2                            6-53  CH.sub.3                                                                         3-CH.sub.3                                                                         4-H O H H H H  4-O                                                                              CH.sub.3                                                                            2,5-(CH.sub.3).sub.2                    __________________________________________________________________________

                  TABLE 7                                                         ______________________________________                                         ##STR54##                                                                    ______________________________________                                    

G¹ to G⁴ in Table 7 are, respectively, as follows;

    __________________________________________________________________________     ##STR55##                                                                     ##STR56##                                                                    Com-                                                                          pound                                                                         No. B X R.sup.4         R.sup.5                                                                          R.sup.6                                                                         (R.sup.7)l                                                                       Y  A                                          __________________________________________________________________________    7-1 G.sup.1                                                                         O                                                                                ##STR57##      H  H H  4-O                                                                               ##STR58##                                 7-2 G.sup.1                                                                         O                                                                                ##STR59##      H  H H  4-O                                                                               ##STR60##                                 7-3 G.sup.1                                                                         O                                                                                ##STR61##      H  H H  4-O                                                                               ##STR62##                                 7-4 G.sup.1                                                                         O                                                                                ##STR63##      H  H H  4-O                                                                               ##STR64##                                 7-5 G.sup.1                                                                         O                                                                                ##STR65##      H  H H  4-O                                                                               ##STR66##                                 7-6 G.sup.1                                                                         O                                                                                ##STR67##      H  H H  4-O                                                                               ##STR68##                                 7-7 G.sup.1                                                                         O                                                                                ##STR69##      H  H H  4-O                                                                               ##STR70##                                 7-8 G.sup.1                                                                         O                                                                                ##STR71##      H  H H  4-O                                                                               ##STR72##                                 7-9 G.sup.1                                                                         O                                                                                ##STR73##      H  H H  4-O                                                                               ##STR74##                                 7-10                                                                              G.sup.1                                                                         O                                                                                ##STR75##      H  H H  4-O                                                                               ##STR76##                                 7-11                                                                              G.sup.1                                                                         O                                                                                ##STR77##      H  H H  4-O                                                                               ##STR78##                                 7-12                                                                              G.sup.1                                                                         O                                                                                ##STR79##      H  H H  4-O                                                                               ##STR80##                                 7-13                                                                              G.sup.1                                                                         O SN(n-C.sub.4 H.sub.9).sub.2                                                                   H  H H  4-O                                                                               ##STR81##                                 7-14                                                                              G.sup.1                                                                         O                                                                                ##STR82##      H  H H  4-O                                                                               ##STR83##                                 7-15                                                                              G.sup.1                                                                         O                                                                                ##STR84##      H  H H  4-O                                                                               ##STR85##                                 7-16                                                                              G.sup.1                                                                         O S(O)N(n-C.sub.4 H.sub.9).sub.2                                                                H  H H  4-O                                                                               ##STR86##                                 7-17                                                                              G.sup.1                                                                         O S(O).sub.2N(n-C.sub.4 H.sub.9).sub.2                                                          H  H H  4-O                                                                               ##STR87##                                 7-18                                                                              G.sup.1                                                                         O S-n-C.sub.4 H.sub.9                                                                           H  H H  4-O                                                                               ##STR88##                                 7-19                                                                              G.sup.1                                                                         O                                                                                ##STR89##      H  H H  4-O                                                                               ##STR90##                                 7-20                                                                              G.sup.1                                                                         O                                                                                ##STR91##      H  H H  4-O                                                                               ##STR92##                                 7-21                                                                              G.sup.2                                                                         O                                                                                ##STR93##      H  H H  4-O                                                                               ##STR94##                                 7-22                                                                              G.sup.3                                                                         O                                                                                ##STR95##      H  H H  4-O                                                                               ##STR96##                                 7-23                                                                              G.sup.4                                                                         O                                                                                ##STR97##      H  H H  4-O                                                                               ##STR98##                                 7-24                                                                              G.sup.1                                                                         O                                                                                ##STR99##      H  H H  4-O                                                                               ##STR100##                                7-25                                                                              G.sup. 1                                                                        O                                                                                ##STR101##     H  H H  4-O                                                                               ##STR102##                                7-26                                                                              G.sup.1                                                                         O                                                                                ##STR103##     H  H H  4-O                                                                               ##STR104##                                7-27                                                                              G.sup.1                                                                         O                                                                                ##STR105##     H  H H  4-O                                                                               ##STR106##                                7-28                                                                              G.sup.1                                                                         O                                                                                ##STR107##     H  H H  4-O                                                                               ##STR108##                                7-329                                                                             G.sup.1                                                                         O                                                                                ##STR109##     H  H H  4-O                                                                               ##STR110##                                7-30                                                                              G.sup.1                                                                         O                                                                                ##STR111##     H  H H  4-O                                                                               ##STR112##                                7-31                                                                              G.sup.1                                                                         O                                                                                ##STR113##     H  H H  4-O                                                                               ##STR114##                                7-32                                                                              G.sup.1                                                                         O                                                                                ##STR115##     H  H H  4-O                                                                               ##STR116##                                7-33                                                                              G.sup.1                                                                         O                                                                                ##STR117##     CH.sub.3                                                                         H H  4-O                                                                               ##STR118##                                7-34                                                                              G.sup.1                                                                         O                                                                                ##STR119##     CH.sub.3                                                                         H H  4-O                                                                               ##STR120##                                7-35                                                                              G.sup.1                                                                         O                                                                                ##STR121##     C.sub.2 H.sub.5                                                                  H H  4-O                                                                               ##STR122##                                7-36                                                                              G.sup.1                                                                         O                                                                                ##STR123##     C.sub.2 H.sub.5                                                                  H H  4-O                                                                               ##STR124##                                7-37                                                                              G.sup.2                                                                         O                                                                                ##STR125##     H  H H  4-O                                                                               ##STR126##                                7-38                                                                              G.sup.2                                                                         O                                                                                ##STR127##     H  H H  4-O                                                                               ##STR128##                                7-39                                                                              G.sup.2                                                                         O                                                                                ##STR129##     H  H H  4-O                                                                               ##STR130##                                7-40                                                                              G.sup.2                                                                         O                                                                                ##STR131##     H  H H  4-O                                                                               ##STR132##                                7-41                                                                              G.sup.2                                                                         O                                                                                ##STR133##     H  H H  4-O                                                                               ##STR134##                                7-42                                                                              G.sup.2                                                                         O                                                                                ##STR135##     H  H H  4-O                                                                               ##STR136##                                7-43                                                                              G.sup.2                                                                         O SN-(n-C.sub.4 H.sub.9).sub.2                                                                  H  H H  4-O                                                                               ##STR137##                                __________________________________________________________________________

When the compound of the present invention is used as an activeingredient of the insecticidal, acaricidal composition, it may be usedas it is without any addition of other ingredients, but usually, it isused in the formulations such as oil formulations, emulsifiableconcentrates, wettable powders, flowable formulations, granules, dusts,aerosols and poisonous baits by mixing it with solid carriers, liquidcarriers, gaseous carriers, baits or the like, and if necessary, byadding thereto surface active agents and/or other adjuvants for theformulation.

These formulations usually contain the present compound as the activeingredient in an amount of from 0.01% to 95% by weight.

The solid carriers usable in the formulations include, for example,clays (such as kaolin clay, diatomaceous earth, synthetic hydratedsilicon dioxide, bentonite, Fubasami clay and acid clay), talcs,ceramics, other inorganic minerals (such as sericite, quartz, sulfur,activated carbon, calcium carbonate and hydrated silica), chemicalfertilizers (such as ammonium sulfate, ammonium phosphate, ammoniumnitrate, urea fertilizer and ammonium chloride), and the like, each inthe form of fine powders or granules. The liquid carriers include, forexample, water, alcohols (such as methanol and ethanol), ketones (suchas acetone and methyl ethyl ketone), aromatic hydrocarbons (such asbenzene, toluene, xylene, ethylbenzene and methylnaphthalene), aliphatichydrocarbons (such as hexane, cyclohexane, kerosene and gas oil), esters(such as ethyl acetate and butyl acetate), nitriles (such asacetonitrile and isobutyronitrile), ethers (such as diisopropyl etherand dioxane), acid amides (such as N,N-dimethylformamide andN,N-dimethylacetamide), halogenated hydrocarbons (such asdichloromethane, trichloroethane and carbon tetrachloride), dimethylsulfoxide, vegetable oils such as soybean oil and cotton seed oil, andthe like. The gaseous carriers, i.e. propellants, include, for example,Flon gas, butane gas, LPG (liquified petroleum gas), dimethyl ether,carbon dioxide gas, and the like.

The surface active agents usable for the emulsification, dispersion,wetting and the like include, for example, anionic surface active agentssuch as the salts of alkyl sulfates, the salts of alkyl(aryl)sulfonicacids, the salts of dialkyl sulfosuccinates, the salts ofpolyoxyethylene alkylaryl ether phosphates and naphthalenesulfonic acid/formaldehyde condensates, and nonionic surface active agents such aspolyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene blockcopolymers, sorbitan fatty acid esters and polyoxyethylene sorbitanfatty acid esters.

As to the adjuvants for the formulation, the stickers and dispersingagents include, for example, casein, gelatin, polysaccharides (such asstarch powder, gum arabic, cellulose derivatives and alginic acid),lignin derivatives, bentonite, saccharides, synthetic water-solublepolymers (such as polyvinyl alcohol, polyvinyl pyrrolidone andpolyacrylic acids) and the like. The stabilizers include, for example,PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol),BHA (a mixture of 2-tert-butyl-4-methoxyphenol and3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfaceactive agents, fatty acids and their esters, and the like.

The substrates for the poisonous baits include, for example, baitcomponents such as grain powders, vegetable essential oils, saccharidesand crystalline cellulose, antioxidants such as dibutylhydroxytolueneand nordihydroguaiaretic acid, preservatives such as dehydroacetic acid,mis-eating inhibitors such as red pepper powders, attractive perfumessuch as cheese perfume and onion perfume, and the like.

The flowable formulations (suspension in water or emulsion in water) areprepared, in general, by finely dispersing 1 to 75% of the activecompound into water containing 0.5 to 15% of a dispersing agent, 0.1 to10% of a dispersing auxiliary (such as protective colloids and compoundscapable of giving thixotropy) and 0 to 10% of a suitable adjuvant (suchas deforming agents, anticorrosives, stabilizers, spreaders, penetrationauxiliaries, antifreezing agents, antibacterial agents and antimoldingagents). It is also possible to prepare the suspension in oil by usingan oil scarcely dissolving the active compound in place of the water.The protective colloids include, for example, gelatin, casein, gums,cellulose ethers, polyvinyl alcohol and the like, and the compoundscapable of giving thixotropy include, for example, bentonite, aluminummagnesium silicate, xanthan gum, polyacrylic acid and the like.

The formulations thus obtained can be used directly or after dilutedwith a diluent such as water. Alternatively, they can be used as amixture with any other agent such as insecticides, acaricides,nematocides, soil-pest controlling agents, insect pest controllingagents, fungicides, herbicides, plant growth regulators, synergists,fertilizers and soil improvers, and also can be used simultaneously withany of these agents without mixing.

When the compound of the present invention is used as the activeingredient of the insecticidal, acaricidal compositions for agriculturaluse, the dosage rate of the active ingredient is usually from 1 g to1000 g per 10 ares. The emulsifiable concentrates, wettable powders,flowable formulations and the like may be diluted with water at theusage, and their application concentration is from 10 ppm to 1000 ppm asthe concentration of the active ingredient. The granules, dusts and thelike are normally applied as they are without any dilution. When theinsecticidal, acaricidal compositions are use for the household use orpublic hygiene, the emulsifiable concentrates, wettable powders,flowable formulations and the like are applied by diluting them withwater to a concentration of the active ingredient of from 0.1 ppm to1000 ppm, while the oil formulations, aerosols, misting agents,poisonous baits and the like are applied as they are.

Since the dosage rate and the application concentration possibly varywith any situations such as the kind of formulations, the seasons, placeand manner of the application, the kind of pests, and the degree ofdamage, they may be increased or decreased irrespective of theabove-mentioned ranges.

The present invention will more fully be described by referringproduction examples, as well as formulation examples and test examples,which are, however, not to limit the present invention.

First, the production examples will be illustrated.

Production Example 1: Preparation of the compound (2-79)

To a stirred mixture of4-[4-(1,1,2,2-tetrafluoroethoxy)phenoxy]benzylamine (359 mg, 1.14 mM),triethylamine (136 mg, 1.35 mM) and toluene (20 ml) was added dropwise asolution (10 ml) of 4-chloro-1,3-dimethylpyrazole-5-carbonyl chloride(200 mg, 1.04 mM) in toluene at 0°-10° C., and the mixture was stirredfor 3 h at room temperature. The mixture was poured into ice water, andthe mixture was extracted with toluene. The extract was washed withsaturated sodium hydrogen carbonate solution, saturated ammoniumchloride solution and brine, dried with magnesium sulfate, andconcentrated in vacuo. The residue was chromatographed over silica gelto giveN-{4-[1,1,2,2,-tetrafluoroethoxy)phenoxy]-benzyl}-4-chloro-1,3-dimethylpyrazole-5-carboxamide(420 mg, 86%) as colorless crystals, m.p. 101.3° C.

Production Example 2: Preparation of the compound (3-90)

In the same manner, 4-chloro-1,3-dimethylpyrazole-5-carboxylic acid (182mg, 1.04 mM), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (200 mg,1.04 mM) and 4-(3-bromo-4-methylthiophenoxy)benzylamine (304 mg, 1.04mM) yieldedN-[4-(3-bromo-4-methylthiophenoxy)-benzyl]-4-chloro-1,3-dimethylpyrazole-5-carboxamide(219 mg, 47%) as colorless crystals, m.p. 117°-119° C.

Production Example 3: Preparation of the compound (7-43)

To a stirred mixture ofN-[4-(4-methylthiophenoxy)benzyl]-4-chloro-1,3-dimethylpyrazole-5-carboxamide(300 mg, 0.746 mM), 4-(N,N-dimethylamino)pyridine (119 mg, 0.970 mM) anddry pyridine (5 ml) was added dropwise N,N-di-n-butylaminosulfenylchloride (190 mg, 0.970 mM) at 0°-10° C., and the mixture was stirredfor 4 h at the room temperature. The mixture was poured into ice water,and the mixture was extracted with dichloromethane. The extract waswashed with saturated ammonium chloride solution(x2) and brine, driedwith sodium sulfate, and concentrated in vacuo. The residue waschromatographed over silica gel to giveN-(N,N-di-n-butylaminosulfenyl)-N-[4-(4-methylthiophenoxy)benzyl]4-chloro-1,3-dimethylpyrazole-5-carboxamide(217 mg, 52%) as a colorless oil, n_(D) ²³.3 1.5748.

Production Example 4: Preparation of4-(3-bromo-4-methylthiophenoxy)benzylamine

To a stirred mixture of lithium aluminum hydride (2.37 g, 62.5 mM) anddry tetrahydrofurane (200 ml) was added dropwise a solution(50 ml) of4-(3-bromo-4-methylthiophenoxy)benzonitrile (2.37 g, 62.5 mM) in drytetrahydrofurane at 0°-10° C., and the mixture was stirred for 1 day atthe room temperature. To this was added tetrahydrofurane (100 ml) andadded dropwise water (10 ml) at 0°-10° C. To the mixture was addedsodium sulfate (100 g), and the mixture was stirred for 30 min at roomtemperature. The mixture was filtered through celite, and the filtratewas concentrated in vacuo to give4-(3-bromo-4-methylthiohenoxy)benzylamine (9.82 g, 97%) as colorlesscrystals, m.p. 75.3° C.

Production Example 5: 4-(3,5-dimethyl-4-methylthiophenoxy)benzonitrile

To a stirred mixture of sodium hydride (1.22 g, 50.9 mM) and dryN,N-dimethylformamide (200 ml) was added a solution (50 ml) of3,5-dimethyl-4-(methylthio)-phenol (9.34 g, 55.5 mM) in dryN,N-dimethylformamide at room temperature, and the mixture was stirredfor 30 min at the same temperature. To this was added4-chlorobenzonitrile (6.37 g, 46.3 mM) and copper(I) chloride (0.5 g),and the mixture was stirred for 12 h at 140°-150° C. The mixture wascooled to the room temperature and this was poured into ice water (500ml). The mixture was extracted with toluene, and the extract was washedwith 5N aq NaOH, water, saturated ammonium chloride solution, water andbrine, dried with magnesium sulfate, and concentrated in vacuo. Theresidue was chromatographed over silica gel to give4-(3,5-dimethyl-4-methylthiophenoxy)benzonitrile (13.03 g, 87%) ascolorless crystals, m.p. 71.8° C.

Production Example 6: Preparation of 4-(4-methylthiophenoxy)propiophenone

20 To a stirred mixture of sodium hydride (1.57 g, 65.3 mM) and dryN,N-dimethylformamide (200 ml) was added dropwise a solution (50 ml) of4-(methylthio)-phenol (71.3 mM) in dry N,N-dimethylformamide at roomtemperature, and the mixture was stirred for 30 min at the sametemperature. To this was added 4-bromoacetophenone dimethylacetal (15.4g, 59.4 mM) and copper(I) chloride (0.5 g) and the mixture was stirredfor 12 h at 140°-150° C. The mixture was cooled to room temperature andpoured into water, and the mixture was extracted with toluene. Theextract was washed with 5N--NaOH, water, saturated ammonium chloridesolution, water and brine, and this was dried with magnesium sulfate andconcentrated in vacuo. The residue was chromatographed over alumina togive 4-(4-methylthiophenoxy)propiophenone dimethylacetal (10.8 g, 57%).To this (5.00 g, 15.7 mM) was added methanol (200 ml), water (50 ml) and2N-H₂ SO₄, and the mixture was stirred for 5 h under reflux. The mixturewas concentrated in vacuo, and the residue was diluted with water. Themixture was extracted with ether, and the extract was washed withsaturated sodium hydrogen carbonate solution, water and brine, driedwith sodium sulfate and concentrated in vacuo.

The residue was chromatographed over silica gel to give4-(4-methylthiophenoxy)propiophenone (2.60 g, 61%) as colorlesscrystals, m.p. 69.4° C.

Production Example 7: Preparation of ethyl4-(4-methylthiophenoxy)benzoate

The mixture of 4-bromothioanisole (10.0 g, 49.2 mM), ethyl4-hydroxybenzoate (8.17 g, 49.2 mM), potassium carbonate (6.80 g, 49.2mM), copper (0.5 g) and xylene (300 ml) was stirred for 24 h underreflux. The mixture was cooled to the room temperature and poured intowater. The mixture was filtered through celite, and the toluene solutionwas washed with water and brine, dried with magnesium sulfate, andconcentrated in vacuo. The residue was chromatographed over silica gelto give ethyl 4-(4-methylthiophenoxy)benzoate (4.86 g, 36%) as colorlesscrystals, m.p. 46.4° C.

Production Example 8: Preparation of 4-(4-methylthiophenoxy)benzylalcohol

To a stirred mixture of lithium aluminum hydride (0.55 g, 14.6 mM) anddry tetrahydrofurane (100 ml) was added a solution (30 ml) of ethyl4-(4-methylthiophenoxy)benzoate (4.00 g, 14.6 mM) in drytetrahydrofurane at 0°-10° C., and the mixture was stirred for 12 h atroom temperature. To this wa added 10% HCl (200 ml) and the mixture wasextracted with toluene. The extract was washed with saturated sodiumhydrogen carbonate solution and brine, dried with magnesium sulfate, andconcentrated in vacuo. The residue was chromatographed over silica gelto give 4-(4-methylthiophenoxy)benzyl alcohol (3.13 g, 87%) as colorlesscrystals, m.p. 103.3° C.

Production Example 9: Preparation of 4-(4-methylthiophenoxy)benzylbromide

To a stirred mixture of phosphorus tribromide (1.20 g, 4.43 mM) and dryether (100 ml) was added a solution (20 ml) of4-(4-methylthiophenoxy)benzyl alcohol (3.00 g, 12.1 mM) in dry ether atthe room temperature, and the mixture was stirred for 12 h at the sametemperature. The mixture was poured into ice water, and the mixture wasextracted with ether. The extract was washed with saturated sodiumhydrogen carbonate solution and brine, dried with magnesium sulfate, andconcentrated in vacuo to give 4-(4-methylthiophenoxy)benzyl bromide(2.39 g, 64%) as colorless crystals, m.p. 32.9° C.

Production Example 10: Preparation of 4-(4-methylthiophenoxy)benzylamine

To a stirred mixture of 28% aq NH₃ (40 ml) and methanol (200 ml) wasadded dropwise a solution (20 ml) of4-(4-methylthiophenoxy)benzylbromide (5.00 g, 16.2 mM) in methanol atroom temperature, and the mixture was stirred for 4 days at the sametemperature. To the mixture was added water (100 ml), and the mixturewas concentrated in vacuo. The residue was diluted with chloroform, andthe mixture was washed with water and brine, dried with sodium sulfate,and concentrated in vacuo. The residue was chromatographed over aluminato give 4-(4-methylthiophenoxy)benzylamine (2.11 g, 53%) as colorlesscrystals, m.p. 61.8° C.

Production Example 11: Preparation of 4-(4-methylthiophenoxy)benzylamine

To a stirred mixture of potassium phthalimide (3.60 g, 19.4 mM) and dryN,N-dimethylformamide (200 ml) was added dropwise a solution of4-(4-methylthiophenoxy)benzylbromide (5.00 g, 16.2 mM) in dryN,N-dimethylformamide at room temperature, the mixture was stirred for 5h at the same temperature. The mixture was poured into water, and themixture was extracted with toluene. The extract was washed with 5N NaOH,water and brine, dried with magnesium sulfate, and concentrated invacuo. The residue was diluted with methanol (200 ml), and to themixture was added dropwise hydrazine monohydrate (1.10 g, 21.1 mM). Themixture was stirred for 6 h under reflux, and this was cooled to theroom temperature and concentrated in vacuo. The residue was diluted withchloroform and the mixture was filtered through celite. The filtrate waswashed with 5N NaOH(x3) and brine(x2), dried with potassium carbonate,and concentrated in vacuo to give 4-(4-methylthiophenoxy)benzylamine(3.02 g, 76%) as colorless crystals, m.p. 61.8° C.

Production Example 12: Preparation of1-[4-(4-methylthiophenoxy)phenyl]propylamine

A mixture of 4-(4-methylthiopheoxy)propiophenone (9.00 g, 33 mM),ammonium acetate (50.9 g, 660 mM), NaBH3CN (2.10 g, 33 mM) and drymethanol (300 ml) was stirred for 3 days at room temperature undernitrogen. To the mixture was added c.HCl until pH<2, and concentrated invacuo. To the residue was added water (200 ml) and ether (200 ml), andthe mixture was stirred for 10 min. To the separated aqueous phase wasadded solid KOH until pH>10, and the mixture was saturated with NaCl.The mixture was extracted with ether, and the extract was dried withsodium sulfate and concentrated in vacuo to give1-[4-(4-methylthiophenoxy)phenyl]propylamine (7.60 g, 84%) as acolorless oil, n_(D) ²⁴.0 1.6027.

In Table 8, there are shown some compounds of the present inventionprepared according to the process or substantially the same procedure inthe Production Examples 1 to 3. The compound numbers are according tothose described in Table 1 to 5.

                  TABLE 8                                                         ______________________________________                                        Compound     Physical                                                         No.          property                                                         ______________________________________                                        1-1          n.sub.D.sup.22.2 1.5779                                          1-2          n.sub.D.sup.22.0 1.5647                                          1-59         n.sub.D.sup.24.2 1.5756                                          1-60         n.sub.D.sup.19.9 1.6187                                          1-61         n.sub.D.sup.19.9 1.5793                                          1-62         n.sub.D.sup.21.7 1.6140                                          1-63         n.sub.D.sup.21.8 1.6076                                          1-64         n.sub.D.sup.22.3 1.5810                                          1-65         n.sub.D.sup.21.9 1.5682                                          2-3          n.sub.D.sup.22.8 1.5378                                          2-10         mp 88-90° C.                                              2-11         n.sub.D.sup.26.2 1.6071                                          2-12         n.sub.D.sup.22.0 1.6045                                          2-13         mp 99.1° C.                                               2-14         n.sub.D.sup.22.8 1.5890                                          2-28         n.sub.D.sup.49.5 1.5655                                          2-31          .sup. n.sub.D.sup.24.9 1.5620*.sup.1                            2-60         n.sub.D.sup.26.3 1.6095                                          2-61         mp 116.7° C.                                              2-68         n.sub.D.sup.21.8 1.6068                                          2-77         mp 118.8° C.                                              2-78         mp 151.1° C.                                              2-79         mp 101.3° C.                                              2-80         n.sub.D.sup.24.3 1.5656                                          2-81         mp 99.0° C.                                               2-82         mp 137.3° C.                                              2-83         n.sub.D.sup.24.1 1.5415                                          2-84          .sup. n.sub.D.sup.24.4 1.6091*.sup.2                            2-85          .sup. n.sub.D.sup.22.3 1.5999*.sup.3                            2-86         n.sub.D.sup. 23.7 1.5466                                         2-87         mp 150.6° C.                                              2-88          .sup. n.sub.D.sup.25.1 1.6105*.sup.4                            2-89         n.sub.D.sup.29.5 1.6087                                          2-94         n.sub.D.sup.22.4 1.5570                                          2-98         mp 137.3° C.                                              2-99         mp 119-121° C.                                             2-100       n.sub.D.sup.22.9 1.5966                                           2-101       viscous liquid                                                    2-102       resinoid                                                          2-103       mp 103-104° C.                                             2-104       mp 151.7° C.                                               2-105       mp 150.6° C.                                               2-106       mp 127.7° C.                                               2-107       mp 76-77.5° C.                                             2-108       mp 87-91° C.                                               2-109       mp 115-119° C.                                             2-110       mp 105.5-107° C.                                           2-111       mp 57.7° C.                                                2-112       n.sub.D.sup.35.5 1.5911                                           2-113       mp 96.8° C.                                                2-114       mp 87.0° C.                                                2-115       mp 81.6° C.                                                2-116       mp 87.7° C.                                                2-117       mp 83-87° C.                                               2-118       mp 87-91° C.                                               2-119       mp 114-119° C.                                             2-120       mp 105.5-107° C.                                           2-121       mp 84-88° C.                                               2-122       n.sub.D.sup.23.7 1.5454                                           2-123       n.sub.D.sup.25.7 1.6021                                           2-124       mp 114-116°  C.                                            2-125       mp 137.8° C.                                               2-126       mp 148.5° C.                                               2-127       mp 111.6° C.                                               2-128       n.sub.D.sup.25.6 1.5992                                           2-129       n.sub.D.sup.25.3 1.5970                                           2-130       mp 136.5° C.                                               2-131       n.sub.D.sup.25.7 1.6131                                           2-132       n.sub.D.sup.23.1 1.6042                                           2-133       n.sub.D.sup.23.0 1.6051                                           2-134       n.sub.D.sup.23.8 1.6038                                           2-135       n.sub.D.sup.23.6 1.5836                                           2-136       n.sub.D.sup.23.1 1.5912                                           2-137       mp 114-117° C.                                             2-138       mp 98-99° C.                                               2-139       n.sub.D.sup.24.1 1.6025                                           2-140       mp 104-106° C.                                             2-141       mp 106.8° C.                                               2-142       mp 117.0° C.                                               2-143       n.sub.D.sup.24.3 1.6068                                           2-144       n.sub.D.sup.26.1 1.6042                                           2-145       n.sub.D.sup.23.5 1.6121                                           2-146       mp 120.9° C.                                               2-147       n.sub.D.sup.26.1 1.5928                                           2-148       n.sub.D.sup.24.2 1.5989                                           2-149       n.sub.D.sup.24.2 1.5826                                           2-150       mp 124.0° C.                                               2-151       mp 91-92° C.                                              3-1          mp 98.6° C.                                               3-2          n.sub.D.sup.21.0 1.6205                                          3-3          n.sub.D.sup. 22.9 1.6039                                         3-4          n.sub.D.sup.22.8 1.6079                                          3-6          n.sub.D.sup.27.4 1.5898                                          3-7          mp 119.5° C.                                              3-8          mp 112.0° C.                                              3-9          mp 99.2° C.                                               3-10         n.sub.D.sup.25.2 1.5827                                          3-11         mp 105.7° C.                                              3-12         n.sub.D.sup.29.0 1.5691                                          3-13         n.sub.D.sup.24.1 1.5775                                          3-14         mp 109.31° C.                                             3-16         n.sub.D.sup.22.9 1.6007                                          3-17         n.sub.D.sup.23.8 1.6292                                          3-46          .sup. n.sub.D.sup.19.9 1.5829*.sup.5                            3-52         mp 116.0° C.                                              3-63         n.sub.D.sup.26.5 1.6017                                          3-64         resinoid                                                         3-65         mp 84.1° C.                                               3-69         mp 121.2° C.                                              3-70         mp 87.1° C.                                               3-71         n.sub.D.sup.23.0 1.5740                                          3-72         n.sub.D.sup.23.1 1.5818                                          3-73         mp 70.5° C.                                               3-74         mp 99-101° C.                                             3-75         mp 96.5° C.                                               3-76         mp 74-77° C.                                              3-77         mp 98.1° C.                                               3-89         mp 106.3° C.                                              3-83         n.sub.D.sup.22.9 1.6004                                          3-86         mp 146.3° C.                                              3-87         mp 112.5° C.                                              3-88         n.sub.D.sup.24.2 1.5899                                          3-89         n.sub.D.sup.36.5 1.5920                                          3-90         mp 117-119° C.                                            3-93         n.sub.D.sup.25.2 1.5873                                          3-94         mp 83.5° C.                                               4-18         mp 127.2° C.                                              5-3          mp 106.4° C.                                              5-14         mp 103.1° C.                                              6-7          mp 144-147° C.                                            6-8          mp 117.0° C.                                              6-10         n.sub.D.sup.23.4 1.6297                                          6-14         n.sub.D.sup.23.8 1.6292                                          6-23         n.sub.D.sup.21.9 1.5869                                          6-50         n.sub.D.sup.23.3 1.5848                                          7-3          n.sub.D.sup.24.5 1.5976                                          7-10         n.sub.D.sup.26.5 1.6014                                          7-21         n.sub.D.sup.25.1 1.5911                                          7-24         n.sub.D.sup.24.1 1.5902                                          7-43         n.sub.D.sup.23.3 1.5748                                          ______________________________________                                         *.sup.1 This compound was allowed to stand at the room temperature for on     week for solidification. mp 78-82° C.                                  *.sup.2 This compound was allowed to stand at the room temperature for on     week for solidification. mp 137.2° C.                                  *.sup.3 This compound was allowed to stand at the room temperature for on     week for solidification. mp 163.8° C.                                  *.sup.4 This compound was allowed to stand at the room temperature for on     week for solidification. mp 87.7° C.                                   *.sup.5 This compound was allowed to stand at the room temperature for on     week for solidification. mp 99-100° C.                            

Then, the formulation examples will be illustrated. All parts are byweight. The compounds of the present invention employed herein are shownwith reference to the compound numbers in Table 1 to 5.

Formulation Example 1 Emulsifiable concentrate

Each 10 parts portion of the Compounds described in Table 1 to 7 wasdissolved into a mixture of 35 parts of xylene and 35 parts ofdimethylformamide. To the resulting solution were added 14 parts ofpolyoxyethylene styrylphenyl ether and 6 parts of calciumdodecylbenzenesulfonate. After blending by full agitation, a 10%emulsifiable concentrate of each Compound was obtained.

Formulation Example 2 Wettable powder

15 Each 20 parts portion of the solid Compounds described in Table 1 to7 was added to a mixture of 4 parts of sodium lauryl sulfate, 2 parts ofcalcium lignisulfonate, 20 parts of finely powdered synthetic hydroussilicon oxide, and 54 parts of diatomaceous earth, and the resultingmixture was blended by agitation using a juice-mixer, thereby to obtaina 20% wettable powder of each Compound.

Formulation Example 3 Dust formulation

Each 1 part portion of the Compounds described in Table 1 to 7 wasdissolved in an adequate amount of acetone. To the resulting solutionwere added 5 parts of finely powdered synthetic hydrous silicon oxide,0.3 part of PAP, and 93.7 parts of clay, and the mixture was blended byagitation in a juice-mixer. Removal of the acetone by evaporation left a1% dust formulation of each Compound.

Formulation Example 4 Flowable formulation

Each 20 parts portion of the Compounds described in Table 1 to 7 and 1.5parts of sorbitan trioleate were mixed with 28.5 parts of an aqueoussolution containing 2 parts of polyvinyl alcohol. The mixture was finelyparticulated (up to not more than 3 μ particle diameter) using a sandgrinder. Thereto were added 40 parts of an aqueous solution containing0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate,and then 10 parts of propylene glycol. The mixture was blended byagitation, to obtain a 20% flowable formulation of each Compound.

Formulation Example 5 Oil formulation

Each 0.1 part portion of the Compounds described in Table 1 to 7 wasdissolved into a mixture of 5 parts of xylene and 5 parts oftrichloroethane. Blending of the solution with 89.9 parts of deodorizedkerosene yielded a 0.1% oil formulation of each Compound.

Then, test examples will be illustrated. The compounds of the presentinvention employed herein are shown with reference to the numbers of thecompounds in Table 1 to 7, and the compounds employed for the comparisonare shown by symbolic letters of the compounds in Table 9.

                                      TABLE 9                                     __________________________________________________________________________    Symbolic                                                                      letter of                                                                     the compound                                                                         Structural formula            remarks                                  __________________________________________________________________________            ##STR138##                   Compound No. 60 described in EP No.                                           234045A.sub.2                            B                                                                                     ##STR139##                   Compound No. 36 described in EP No.                                           289879-A                                 C                                                                                     ##STR140##                   Compound No. 19 described in EP No.                                           289879-A                                 D                                                                                     ##STR141##                   Compound included in EP No.              __________________________________________________________________________                                         289879-A                             

Test Example 1: Test against carmine mites (Tetranychus cinnabarinu))

Potted vineless kidney beans plants 7 days after sowing (at the stage ofprimordial leaves) were parasitized by 10 female adult carmine mites perleaf, and placed in an incubator at a temperature of 25° C. After 6days, an emulsifiable concentrate of a test compound formulatedaccording to the Formulating Example 1 was diluted with water to 500 ppmconcentration of the active ingredient, and the diluted emulsion wassprayed to the potted plants on a turn table in an amount of 15 ml perpot. At the same time, 2 ml of the emulsion was treated on the pot soil.After 8 days, the damaged level of each plant by the mites was observed.The efficacy was judged according to the following criteria:

-: Almost no damage was observed,

+: Slight damage was observed,

++: Similar degree of damage as that of the untreated was observed.

The results are shown in Table 10.

                  TABLE 10                                                        ______________________________________                                               Test                                                                          Compound                                                                              effect                                                         ______________________________________                                               1-1     --                                                                    1-2     --                                                                    1-59    --                                                                    1-60    --                                                                    1-61    --                                                                    1-62    --                                                                    1-63    --                                                                    1-64    --                                                                    1-65    --                                                                    2-3     --                                                                    2-10    --                                                                    2-11    --                                                                    2-12    --                                                                    2-13    --                                                                    2-14    --                                                                    2-28    --                                                                    2-31    --                                                                    2-60    --                                                                    2-61    --                                                                    2-77    --                                                                    2-78    --                                                                    2-79    --                                                                    2-80    --                                                                    2-81    --                                                                    2-82    --                                                                    2-83    --                                                                    2-84    --                                                                    2-85    --                                                                    2-88    --                                                                    2-89    --                                                                    2-94    --                                                                    2-98    --                                                                    2-99    --                                                                     2-100  --                                                                     2-101  --                                                                     2-102  --                                                                     2-103  --                                                                     2-104  --                                                                     2-106  --                                                                     2-107  --                                                                     2-108  --                                                                     2-109  --                                                                     2-110  --                                                                     2-111  --                                                                     2-112  --                                                                     2-113  --                                                                     2-114  --                                                                     2-115  --                                                                     2-116  --                                                                     2-117  --                                                                     2-118  --                                                                     2-119  --                                                                     2-120  --                                                                     2-121  --                                                                     2-122  --                                                                     2-123  --                                                                     2-129  --                                                                     2-132  --                                                                     2-133  --                                                                     2-134  --                                                                     2-135  --                                                                     2-138  --                                                                     2-140  --                                                                     2-141  --                                                                     2-142  --                                                                     2-144  --                                                                     2-145  --                                                                     2-147  --                                                                     2-148  --                                                                     2-149  --                                                                     2-150  --                                                                     2-151  --                                                                    3-1     --                                                                    3-2     --                                                                    3-3     --                                                                    3-4     --                                                                    3-6     --                                                                    3-11    --                                                                    3-12    --                                                                    3-13    --                                                                    3-14    --                                                                    3-16    --                                                                    3-17    --                                                                    3-46    --                                                                    3-52    --                                                                    3-63    --                                                                    3-64    --                                                                    3-65    --                                                                    3-69    --                                                                    3-70    --                                                                    3-71    --                                                                    3-72    --                                                                    3-73    --                                                                    3-74    --                                                                    3-75    --                                                                    3-76    --                                                                    3-77    --                                                                    3-78    --                                                                    3-83    --                                                                    3-86    --                                                                    3-88    --                                                                    3-89    --                                                                    3-90    --                                                                    3-93    --                                                                    3-94    --                                                                    4-18    --                                                                    5-14    --                                                                    6-7     --                                                                    6-14    --                                                                    6-23    --                                                                    6-50    --                                                                    7-3     --                                                                    7-10    --                                                                    7-21    --                                                                    7-42    --                                                                    7-43    --                                                             ______________________________________                                    

Test Example 2: Insecticidal test against common mosquitos (Culexpipiens pallens)

A test compound was formulated to an emulsifiable concentrate inaccordance with the Formulation Example 1, and the concentrate wasdiluted with water by 200 times. then, 2 ml of the resulting emulsionwas added in 98 ml of ion-exchanged water to obtain a liquid having anactive ingredient concentration of 10 ppm. Into the resulting liquid, 20larvae of common mosquitos in mature instar were released, and themortality at one day later was investigated.

The insecticidal activity was judged with the following criteria:

a: Mortality rate of not less than 90%.

b: Mortality rate between not less than 10% and less than 90%.

c: Mortality rate of less than 10%.

The results are shown in Table 11.

                  TABLE 11                                                        ______________________________________                                               Test                                                                          Compound                                                                              Mortality                                                      ______________________________________                                               1-1     a                                                                     1-2     a                                                                     1-59    a                                                                     1-62    a                                                                     1-63    a                                                                     1-64    a                                                                     1-65    a                                                                     2-3     a                                                                     2-10    a                                                                     2-11    a                                                                     2-31    a                                                                     2-60    a                                                                     2-68    a                                                                     2-77    a                                                                     2-78    a                                                                     2-79    a                                                                     2-80    a                                                                     2-81    a                                                                     2-82    a                                                                     2-83    a                                                                     2-84    a                                                                     2-85    a                                                                     2-86    a                                                                     2-87    a                                                                     2-88    a                                                                     2-89    a                                                                     2-98    a                                                                     2-99    a                                                                      2-100  a                                                                      2-102  a                                                                      2-103  a                                                                      2-106  a                                                                      2-107  a                                                                      2-108  a                                                                      2-109  a                                                                      2-110  a                                                                      2-111  a                                                                      2-112  a                                                                      2-113  a                                                                      2-114  a                                                                      2-115  a                                                                      2-116  a                                                                      2-117  a                                                                      2-118  a                                                                      2-119  a                                                                      2-120  a                                                                      2-121  a                                                                      2-122  a                                                                      2-123  a                                                                      2-129  a                                                                      2-131  a                                                                      2-133  a                                                                      2-135  a                                                                      2-138  a                                                                      2-140  a                                                                      2-141  a                                                                      2-142  a                                                                      2-144  a                                                                      2-145  a                                                                      2-146  a                                                                      2-147  a                                                                      2-148  a                                                                      2-151  a                                                                     3-1     a                                                                     3-3     a                                                                     3-4     a                                                                     3-6     a                                                                     3-7     a                                                              ______________________________________                                               Test                                                                          Compound                                                                              effect                                                         ______________________________________                                                3-14   a                                                                     3-46    a                                                                     3-63    a                                                                     3-64    a                                                                     3-65    a                                                                     3-69    a                                                                     3-70    a                                                                     3-71    a                                                                     3-72    a                                                                     3-73    a                                                                     3-74    a                                                                     3-75    a                                                                     3-76    a                                                                     3-77    a                                                                     3-78    a                                                                     3-86    a                                                                     3-87    a                                                                     3-88    a                                                                     3-89    a                                                                     3-90    a                                                                     3-93    a                                                                     3-94    a                                                                     6-7     a                                                                     6-14    a                                                                     6-50    a                                                                     7-2     a                                                                     7-3     a                                                                     7-9     a                                                                     7-10    a                                                                     7-15    a                                                                     7-21    a                                                                     7-29    a                                                                     7-30    a                                                                     7-31    a                                                                     7-32    a                                                                     7-37    a                                                                     7-39    a                                                                     7-40    a                                                                     7-41    a                                                                     7-42    a                                                                     7-43    a                                                                     B       c                                                                     C       c                                                              ______________________________________                                    

Test Examples 3: Insecticidal test against diamondback moths (Plutellaxylostella)

An emulsifiable concentrate of a test compound formulated according tothe Formulating Example 1 was diluted with water to make an emulsion(corresponding to 50 ppm concentration). Two of radish shoots (5-6 daysafter sowing) were immersed into the emulsion for 30 minutes, thenair-dried, and placed in a cage in which a lot number of wild, adultdiamondback moths of 1-3 day age after emergence have been released, toallow them to lay eggs. At the time of 100-150 eggs laid on each shoot,the shoots were taken out of the cage, and placed in a polyethylene cupof 5.5 cm diameter. The mortality of the larvae after hatching wasobserved. (two replications)

The mortalities were shown in 3 degrees as mentioned below:

a: 100%,

b: not less than 70%, but less than 100%,

c: less than 70%.

The results are shown in Table 12.

                  TABLE 12                                                        ______________________________________                                               Test                                                                          Compound                                                                              Mortality                                                      ______________________________________                                               2-10    a                                                                     2-11    a                                                                     2-12    a                                                                     2-13    a                                                                     2-14    a                                                                     2-31    a                                                                     2-60    a                                                                     2-61    a                                                                     2-68    a                                                                     2-77    a                                                                     2-79    a                                                                     2-80    a                                                                     2-84    a                                                                     2-88    a                                                                     2-89    a                                                                      2-108  a                                                                      2-109  a                                                                      2-110  a                                                                      2-111  a                                                                      2-112  a                                                                      2-113  a                                                                      2-114  a                                                                      2-115  a                                                                      2-116  a                                                                      2-117  a                                                                      2-118  a                                                                      2-119  a                                                                      2-120  a                                                                      2-121  a                                                                      2-123  a                                                                      2-131  a                                                                      2-133  a                                                                      2-135  a                                                                      2-138  a                                                                      2-140  a                                                                      2-141  a                                                                      2-142  a                                                                      2-144  a                                                                      2-145  a                                                                      2-151  a                                                                     3-14    a                                                                     3-16    a                                                                     3-63    a                                                                     3-64    a                                                                     3-65    a                                                                     3-72    a                                                                     3-73    a                                                                     3-76    a                                                                     3-78    a                                                                     3-87    a                                                                     3-90    a                                                                     3-93    a                                                                     3-94    a                                                                     5-3     a                                                                     6-8     a                                                                     7-21    a                                                                     7-42    a                                                                     7-43    a                                                                     A       c                                                                     B       c                                                                     C       c                                                                     D       c                                                              ______________________________________                                    

Test Example 4: Insecticidal test against tobacco cutworms (Spodopteralitura)

A test compound was formulated to an emulsifiable concentrate inaccordance with the Formulation Example 1, and the concentrate wasdiluted with water by 200 times to obtain an emulsion containing 500 ppmof the test compound. On the other hand, 13 g of an artificial diet fortobacco cutworm was prepared in a polyethylene cup having a diameter of11 cm, and was impregnated with 2 ml of the emulsion obtained above. Tenfourth instar larvae of tobacco cutworms were released therein, and sixdays later, the mortality was determined (two replications). The damagedlevel of the artificial diet was also investigated in parallel. Thedamaged level was judged with the following criteria:

-: Almost no damage was observed.

+: Damage was observed.

++: Damage was heavy and the artificial diet scarcely remained.

The results are shown in Table 13.

                  TABLE 13                                                        ______________________________________                                        Test                     Damage                                               Compound        Mortality                                                                              of diet                                              ______________________________________                                        1-62            100      --                                                   1-63            100      --                                                   1-64            100      --                                                   1-65            100      --                                                   2-3             100      --                                                   2-10            100      --                                                   2-11            100      --                                                   2-31            100      --                                                   2-60            100      --                                                   2-61            100      --                                                   2-68            100      --                                                   2-77            100      --                                                   2-78            100      --                                                   2-80            100      --                                                   2-81            100      --                                                   2-82            100      --                                                   2-83            100      --                                                   2-84            100      --                                                   2-85            100      --                                                   2-88            100      --                                                   2-89            100      --                                                    2-103          100      --                                                    2-106          100      --                                                    2-107          100      --                                                    2-108          100      --                                                    2-109          100      --                                                    2-110          100      --                                                    2-111          100      --                                                    2-112          100      --                                                    2-113          100      --                                                    2-114          100      --                                                    2-115          100      --                                                    2-116          100      --                                                    2-117          100      --                                                    2-118          100      --                                                    2-119          100      --                                                    2-120          100      --                                                    2-121          100      --                                                    2-122          100      --                                                    2-123          100      --                                                    2-127          100      --                                                    2-129          100      --                                                    2-131          100      --                                                    2-133          100      --                                                    2-135          100      --                                                    2-138          100      --                                                    2-140          100      --                                                    2-141          100      --                                                    2-142          100      --                                                    2-144          100      --                                                    2-145          100      --                                                    2-146          100      --                                                    2-147          100      --                                                    2-148          100      --                                                    2-149          100      --                                                    2-150          100      --                                                    2-151          100      --                                                   3-1             100      --                                                   3-3             100      --                                                   3-4             100      --                                                   3-14            100      --                                                   3-46            100      --                                                   3-63            100      --                                                   3-65            100      --                                                   3-72            100      --                                                   3-73            100      --                                                   3-74            100      --                                                   3-75            100      --                                                   3-76            100      --                                                   3-78            100      --                                                   3-87            100      --                                                   3-88            100      --                                                   3-90            100      --                                                   3-94            100      --                                                   6-7             100      --                                                   6-23            100      --                                                   6-50            100      --                                                   7-21            100      --                                                   A                95      +                                                    B                50      +                                                    C                0       +                                                    D                10      ++                                                   ______________________________________                                    

Test Example 5: Insecticidal test against houseflies (Musca clomestica)

A filter paper was taken into a polyethylene cup (a diameter of 5.5 cm)at the bottom. The emulsifiable concentrate of a test compound which wasprepared in accordance with the Formulation Example 1 was diluted withwater by 200 times to obtain an emulsion containing ppm of the testcompound, and 0.7 ml of the emulsion was dropped on the filter paper.Further, about 30 mg of sugar was placed there as a bait. Ten adultfemales of housefly were released in the cup which was then capped. Oneday later, the mortality was determined.

The results are shown in Table 14.

                  TABLE 14                                                        ______________________________________                                               Test                                                                          Compound                                                                              Mortality                                                      ______________________________________                                               2-31    100                                                                   2-60    100                                                                   2-61    100                                                                   2-68    100                                                                   2-77    100                                                                   2-78    100                                                                   2-80    100                                                                   2-84    100                                                                   2-88    100                                                                   2-89    100                                                                    2-107  100                                                                    2-108  100                                                                    2-110  100                                                                    2-111  100                                                                    2-112  100                                                                    2-113  100                                                                    2-114  100                                                                    2-116  100                                                                    2-118  100                                                                    2-120  100                                                                    2-121  100                                                                    2-122  100                                                                    2-135  100                                                                    2-141  100                                                                    2-142  100                                                                    2-144  100                                                                    2-145  100                                                                    2-151  100                                                                   3-1     100                                                                   3-3     100                                                                   3-4     100                                                                   3-64    100                                                                   3-65    100                                                                   3-73    100                                                                   3-75    100                                                                   3-78    100                                                                   3-90    100                                                                   4-18    100                                                                   7-21    100                                                                   7-42    100                                                                   7-43    100                                                                   A        0                                                                    B        0                                                                    C        0                                                             ______________________________________                                    

What is claimed is:
 1. An amide compound represented by the formula of##STR142## wherein R¹ is a hydrogen atom, an alkyl group of 1-4 carbonsor a haloalkyl group of 1-4 carbons; R² and R³ independently are ahydrogen atom, a halogen atom, an alkyl group of 1-6 carbons, acycloalkyl group of 3-6 carbons, a haloalkyl group of 1-6 carbons, aphenyl group or an alkoxy group of 1-6 carbons,R⁴ is a hydrogen atom, analkyl group of 1-4 carbons or a group represented by the formula of

    --S(O).sub.m R.sup.11 ;

R⁵ is a hydrogen atom, an alkyl group of 1-4 carbons or a cyano group;R⁶ is a hydrogen atom or an alkyl group of 1-4 carbons; R⁷ is a same ordifferent, a hydrogen atom, a halogen atom or an alkyl group of 1-4carbons;A is the group represented by the formula of ##STR143## R⁸ is ahalogen atom, an alkyl group of 1-8 carbons, a haloalkyl group of 1-8carbons, a haloalkoxy group of 1-8 carbons, an alkylthio group of 1-8carbons, a haloalkylthio group of 1-8 carbons, an alkenylthio group of2-8 carbons, a haloalkenylthio group of 2-8 carbons, an alkynylthiogroup of 2-8 carbons, an alkylsulfinyl group of 1-8 carbons, analkylsulfonyl group of 1-8 carbons; R⁹ is a haloalkoxy group of 1-8carbons, an alkylthio group of 1-8 carbons, a haloalkylthio group of 1-8carbons, an alkenylthio group of 2-8 carbons, a haloalkenylthio group of2-8 carbons, an alkynylthio group of 2-8 carbons, an alkylsulfinyl groupof 1-8 carbons, an alkylsulfonyl group of 1-8 carbons, Each R¹⁰ is asame or different, a halogen atom, an alkyl group of 1-8 carbons, ahaloalkyl group of 1-8 carbons; provided that R⁸ and R¹⁰ may be linkedat their ends, when they are adjacent each other, to form a saturatedfive-membered ring which contains 0-2 oxygen atom therein; R¹¹ is is analkyl group of 1-18 carbons, a haloalkyl group of 1-18 carbons, or agroup represented by the formula of ##STR144## or the formula of##STR145## R¹² is a hydrogen atom, an alkyl group of 1-4 carbons or ahaloalkyl group of 1-4 carbons; R¹³ is a same or different, a hydrogenatom, a halogen atom, an alkyl group of 1-4 carbons, a haloalkyl groupof 1-4 carbons, an alkoxy group of 1-4 carbons, a haloalkoxy group of1-4 carbons, an alkythio group of 1-4 carbons, a haloalkylthio group of1-4 carbons, an alkylsulfinyl group of 1-4 carbons, a haloalkylsulfinylgroup of 1-4 carbons, an alkylsulfonyl group of 1-4 carbons, ahaloalkylsulfony group of 1-4 carbons, an alkylsulfonyloxy group of 1-4carbons, a haloalkylsulfonyloxy group of 1-4 carbons, nitro or cyanogroup; R¹⁴ is an alkyl group of 1-8 carbons, a haloalkyl group of 1-8carbons, an alkoxyalkyl group of 3-8 total carbons or a(haloalkoxy)alkyl group of 3-8 total carbons; R¹⁵ is an alkyl group of1-8 carbons, a haloalkyl group of 1-8 carbons, an alkoxyalkyl group of3-8 total carbons, a (haloalkoxy)alkyl group of 3-8 total carbons or agroup represented by the formula of ##STR146## provided that R¹⁴ and R¹⁵may be linked at their ends to form a saturated or unsaturated five- orsix-membered ring which contains 0-2 oxygen or sulfur atoms therein andmay be substituted with a halogen atom, an alkyl group of 1-4 carbons,an alkoxy group of 1-4 carbons or an alkylthio group of 1-4 carbons; R¹⁶is a hydrogen atom, an alkyl group of 1-8 carbons, a haloalkyl group of1-8 carbons, an alkoxyalkyl group of 2-8 total carbons or a(haloalkoxy)alkyl group of 2-8 total carbons; R¹⁷ is an alkyl group of1-18 carbons, a haloalkyl group of 1-18 carbons, an alkoxyalkyl group of3-18 total carbons, a (haloalkoxy)-alkyl group of 3-18 total carbons, analkoxyhaloalkyl group of 3-18 total carbons, an alkylthioalkyl group of3-18 total carbons, a (haloalkylthio)alkyl group of 3-18 total carbons,a cycloalkyl group of 3-8 carbons which may be substituted with an alkylgroup of 1-10 carbons, a cycloalkyl group of 3-8 carbons substitutedwith a haloalkyl group of 1-10 carbons, a halocycloalkyl group of 3-8carbons which may be substituted with an alkyl group of 1-10 carbons, acycloalkyl group of 3-8 carbons substituted with an alkoxy group of 1-10carbons, or a cycloalkyl group of 3-8 carbons substituted with ahaloalkoxy group of 1-10 carbons; W is an oxygen atom, a sulfur atom, asulfinyl group or single bond; l is an integer of 1 or 2; m is aninteger of 0-2; n is an integer of 1-4; p is an integer of 1-5; q is aninteger of 0-10; X is an oxygen atom or a sulfur atom; Y is an oxygenatom, a sulfur atom, a sulfinyl, sulfonyl or methylene group.
 2. Anamide compound represented by the formula of ##STR147## wherein R¹ is analkyl group of 1-4 carbons or a haloalkyl group of 1 4 carbons; R² andR³ independently are a hydrogen atom, a halogen atom, an alkyl group of1-6 carbons, a cycloalkyl group of 3-6 carbons, a haloalkyl group of 1-6carbons, a phenyl group or an alkoxy group of 1-6 carbons,R⁴ is ahydrogen atom or an alkyl group of 1-4 carbons R⁵ and R⁶ independentlyare a hydrogen atom or an alkyl group of 1-4 carbons; R⁷ is a hydrogenatom, a halogen atom or an alkyl group of 1-4 carbons;A is the grouprepresented by the formula of ##STR148## R⁸ is a halogen atom, an alkylgroup of 1-8 carbons, a haloalkyl group of 1-8 carbons, a haloalkoxygroup of 1-8 carbon an alkylthio group of 1-8 carbons, a haloalkylthiogroup of 1-8 carbons, an alkenylthio group of 2-8 carbons, analkynylthio group of 2-8 carbons, an alkylsulfinyl group of 1-8 carbons,an alkylsulfonyl group of 1-8 carbons; R⁹ is a haloalkoxy group of 1-8carbons, an alkylthio group of 1-8 carbons, a haloalkylthio group of 1-8carbons, an alkenylthio group of 2-8 carbons, an alkynylthio group of2-8 carbons, an alkylsulfinyl group of 1-8 carbons, an alkylsulfonylgroup of 1-8 carbons, Each R¹⁰ is a halogen atom, an alkyl group of 1-8carbons, a haloalkyl group of 1-8 carbons; provided that R⁸ and R¹⁰ maybe linked at their ends, when they are adjacent each other, to form asaturated five-membered ring which contains 0-2 oxygen atom therein; Xis an oxygen atom or a sulfur atom; Y is an oxygen atom, a sulfur atom,a sulfinyl, sulfonyl or methylene group.
 3. An amide compound accordingto claim 1, wherein R⁴ is a hydrogen atom.
 4. An amide compoundaccording to claim 3, wherein R⁸ and R⁹ independently of one another areeach is an alkylthio group of 1-8 carbons, a haloalkylthio group of 18carbons, an alkenylthio group of 2-8 carbons, a haloalkenylthio group of2-8 carbons, an alkynylthio group of 2-8 carbons, an alkoxyalkyl groupof 2-8 total carbons, an alkylsulfinyl group of 1-8 carbons, ahaloalkylsulfinyl group of 1-8 carbons;R¹⁰ is a hydrogen or halogenatom, or an alkyl group of 1-3 carbons or a haloalkyl group of 1-3carbons and X is an oxygen atom.
 5. The compound according to claim 1which isN-[4-(4-methylthiophenoxy)benzyl]-1,3-dimethylpyrazole-5-carboxamide.(2-10)
 6. The compound according to claim 1 which isN-[4-(4-methylthiophenoxy)benzyl]-1,3,4-trimethylpyrazole-5-carboxamide.(2-78)
 7. The compound according to claim 1 which isN-[4-(4-methylthiophenoxy)benzyl]-1,5-dimethylpyrazole-3-carboxamide.(2-88)
 8. The compound according to claim 1 which isN-[4-(4-methylthiophenoxy)benzyl]-4-chloro-1,3-dimethylpyrazole-5-carboxamide.(2-77)
 9. An insecticidal and/or acaricidal composition which comprisesas an active ingredient an insecticidally and/or acaricidally effectiveamount of an amide compound according to claim 1, and an inert carrieror diluent.
 10. A method for exterminating insects and/or acarids whichcomprises applying as an active ingredient an insecticidally and/oracaricidally effective amount of an amide compound according to claim 1to the locus where insects and/or acarids propagate.